CN106232608A - Novel epoxide, mixture, compositions and the cured product containing described epoxide, and its preparation method and application - Google Patents
Novel epoxide, mixture, compositions and the cured product containing described epoxide, and its preparation method and application Download PDFInfo
- Publication number
- CN106232608A CN106232608A CN201580020302.8A CN201580020302A CN106232608A CN 106232608 A CN106232608 A CN 106232608A CN 201580020302 A CN201580020302 A CN 201580020302A CN 106232608 A CN106232608 A CN 106232608A
- Authority
- CN
- China
- Prior art keywords
- formula
- epoxide
- mentioned
- alkyl
- integer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000002118 epoxides Chemical class 0.000 title claims abstract description 298
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 175
- 239000002131 composite material Substances 0.000 claims abstract description 169
- 238000006243 chemical reaction Methods 0.000 claims abstract description 99
- 229910000077 silane Inorganic materials 0.000 claims abstract description 69
- 150000001875 compounds Chemical class 0.000 claims abstract description 65
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 45
- 125000002769 thiazolinyl group Chemical group 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 41
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000945 filler Substances 0.000 claims abstract description 19
- 230000009477 glass transition Effects 0.000 claims abstract description 15
- -1 methoxyl group Chemical group 0.000 claims description 169
- 239000000463 material Substances 0.000 claims description 142
- 125000001424 substituent group Chemical group 0.000 claims description 113
- 125000000217 alkyl group Chemical group 0.000 claims description 85
- 125000004432 carbon atom Chemical group C* 0.000 claims description 74
- 239000002904 solvent Substances 0.000 claims description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 61
- 229910052760 oxygen Inorganic materials 0.000 claims description 57
- 125000003545 alkoxy group Chemical group 0.000 claims description 54
- 239000000835 fiber Substances 0.000 claims description 52
- 125000005842 heteroatom Chemical group 0.000 claims description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims description 52
- 239000001257 hydrogen Substances 0.000 claims description 52
- 229910052717 sulfur Inorganic materials 0.000 claims description 52
- 125000002015 acyclic group Chemical group 0.000 claims description 51
- 239000003365 glass fiber Substances 0.000 claims description 50
- 239000010954 inorganic particle Substances 0.000 claims description 40
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 34
- 125000001931 aliphatic group Chemical group 0.000 claims description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 23
- 239000004065 semiconductor Substances 0.000 claims description 23
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 229920001971 elastomer Polymers 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 239000005060 rubber Substances 0.000 claims description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 125000002723 alicyclic group Chemical group 0.000 claims description 16
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 15
- 229920003986 novolac Polymers 0.000 claims description 15
- 125000003368 amide group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 14
- 239000004305 biphenyl Substances 0.000 claims description 12
- 235000010290 biphenyl Nutrition 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 12
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 12
- 239000012776 electronic material Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 8
- 125000005647 linker group Chemical group 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000003973 paint Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- PEQHIRFAKIASBK-UHFFFAOYSA-N tetraphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PEQHIRFAKIASBK-UHFFFAOYSA-N 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 5
- 150000001334 alicyclic compounds Chemical class 0.000 claims description 5
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000003566 sealing material Substances 0.000 claims description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000012784 inorganic fiber Substances 0.000 claims description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 4
- 229920002577 polybenzoxazole Polymers 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- RUGHUJBHQWALKM-UHFFFAOYSA-N 1,2,2-triphenylethylbenzene Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C(C=1C=CC=CC=1)C1=CC=CC=C1 RUGHUJBHQWALKM-UHFFFAOYSA-N 0.000 claims description 3
- 229910017083 AlN Inorganic materials 0.000 claims description 3
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- 229920000139 polyethylene terephthalate Polymers 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 230000006872 improvement Effects 0.000 abstract description 13
- 238000012545 processing Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000008719 thickening Effects 0.000 abstract 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 108
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 60
- 239000000047 product Substances 0.000 description 51
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 50
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 42
- 238000003756 stirring Methods 0.000 description 38
- 239000002585 base Substances 0.000 description 37
- 239000007795 chemical reaction product Substances 0.000 description 37
- 239000003795 chemical substances by application Substances 0.000 description 37
- 238000002156 mixing Methods 0.000 description 37
- 238000005160 1H NMR spectroscopy Methods 0.000 description 36
- 238000005481 NMR spectroscopy Methods 0.000 description 36
- 239000012043 crude product Substances 0.000 description 34
- 229910052786 argon Inorganic materials 0.000 description 30
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 29
- 229910003446 platinum oxide Inorganic materials 0.000 description 29
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 29
- 239000007789 gas Substances 0.000 description 27
- 229940106691 bisphenol a Drugs 0.000 description 24
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 150000002431 hydrogen Chemical class 0.000 description 18
- 239000003822 epoxy resin Substances 0.000 description 17
- 229920000647 polyepoxide Polymers 0.000 description 17
- 238000006735 epoxidation reaction Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 238000007711 solidification Methods 0.000 description 16
- 230000008023 solidification Effects 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 12
- 229910010272 inorganic material Inorganic materials 0.000 description 11
- 239000011147 inorganic material Substances 0.000 description 11
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- XQNYSQWXELMGHL-UHFFFAOYSA-N C1(CCCCC1)C12C(C=CC=C1)(C1=CC=CC=C1)O2 Chemical compound C1(CCCCC1)C12C(C=CC=C1)(C1=CC=CC=C1)O2 XQNYSQWXELMGHL-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000011152 fibreglass Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 5
- 150000002460 imidazoles Chemical class 0.000 description 5
- 150000002790 naphthalenes Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 208000037656 Respiratory Sounds Diseases 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 239000004848 polyfunctional curative Substances 0.000 description 4
- 150000008442 polyphenolic compounds Chemical class 0.000 description 4
- 238000006884 silylation reaction Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 150000002927 oxygen compounds Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- YXWFTAHVYOBABK-UHFFFAOYSA-N 3-isocyanatopropyl(trimethyl)silane Chemical class C[Si](C)(C)CCCN=C=O YXWFTAHVYOBABK-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 2
- 229920004934 Dacron® Polymers 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000011469 building brick Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- STLZCUYBVPNYED-UHFFFAOYSA-N chlorbetamide Chemical compound OCCN(C(=O)C(Cl)Cl)CC1=CC=C(Cl)C=C1Cl STLZCUYBVPNYED-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical group C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- CPEOJEBZAIYHGD-UHFFFAOYSA-N 1,2-diazacycloundecene Chemical compound C1CCCCN=NCCCC1 CPEOJEBZAIYHGD-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HWRRQRKPNKYPBW-UHFFFAOYSA-N 2,4-dimethylcyclohexan-1-amine Chemical compound CC1CCC(N)C(C)C1 HWRRQRKPNKYPBW-UHFFFAOYSA-N 0.000 description 1
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- GNJLVMKERYSIAI-UHFFFAOYSA-N 4,5,6,7-tetrabromo-3,3-bis(4-hydroxyphenyl)-2-benzofuran-1-one Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C(C(Br)=C(Br)C(Br)=C2Br)=C2C(=O)O1 GNJLVMKERYSIAI-UHFFFAOYSA-N 0.000 description 1
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 229920002732 Polyanhydride Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- WXUZQTFPERWSEC-UHFFFAOYSA-N [O].C(C1CO1)OCC1CO1 Chemical compound [O].C(C1CO1)OCC1CO1 WXUZQTFPERWSEC-UHFFFAOYSA-N 0.000 description 1
- DPRMFUAMSRXGDE-UHFFFAOYSA-N ac1o530g Chemical compound NCCN.NCCN DPRMFUAMSRXGDE-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- ILOIZDYWQDTUNU-UHFFFAOYSA-N ethoxy(3-isocyanatopropyl)silane Chemical class CCO[SiH2]CCCN=C=O ILOIZDYWQDTUNU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to the epoxide of novelty, the method preparing described epoxide, comprise compositions and the cured product of described epoxide, and application, wherein said compound display excellent heat resistance is specifically, low-thermal-expansion character and high glass-transition temperature increase effect (include do not show glass transition temperature without Tg's), anti-flammability and processing characteristics are specifically, without the thickening controlling of independent silane coupler, and there is the fragility of improvement in the composite.According to an aspect of the present invention, it is provided that: epoxide, described epoxide has at least one non-reacted silicyl, thiazolinyl or a combination thereof and at least two epoxide group and at least one alkoxysilyl；The method preparing epoxide by alkoxysilyl and aIkylsilyl groups；Epoxy composite including described epoxide；And cured product.The epoxy composite of the novel epoxide comprising the present invention presents the thermostability of enhancing i.e., because by chemical reaction between alkoxysilyl in chemical reaction between alkoxysilyl and filler and complex and/or cured product, form chemical bond, so glass transition temperature increases the CTE of the epoxy compound of effect and reduction.Additionally, because introducing alkoxysilyl, the epoxy composite of the present invention presents the anti-flammability of excellence.Additionally, in curing reaction, can easily control the thickening of the epoxy composite of the present invention.In addition, the cured product of epoxy composite presents the fragility of improvement.
Description
Technical field
The present invention relates to the epoxide of novelty, when for by solidification comprise epoxide and filler (fiber and/
Or inorganic particle) compositions and time in the composite that obtains, described epoxide present improvement processing characteristics and/or
Fragility and excellent heat resistance, relate to comprising the mixture of described epoxide, compositions and cured product, relate to epoxidation
The preparation method and applications of compound.Specifically, in composite as above, the present invention relates to the epoxidation of novelty
Compound, described epoxide has excellent heat resistance, and specifically low thermal coefficient of expansion and high glass-transition temperature (comprises not
Present glass transition temperature without Tg's), flame-retardant nature and processing characteristics, specifically controllable-viscosity and without independent silane
Coupling agent, and there is the fragility of improvement, relate to comprising the mixture of described epoxide, compositions and cured product, relate to
The preparation method and applications of epoxide.
Background technology
The thermal coefficient of expansion of the epoxide of solidification is several times to tens times of ceramic material and thermal expansion metal coefficient.Cause
This, in the case of associated with epoxy material and inorganic material or metal, because between epoxy material and inorganic material or epoxy material
Thermal coefficient of expansion between material and metal is different, significantly limit performance and the processing characteristics of assembly.Such as, in semiconductor packages
In the case of Deng, when silicon wafer and epoxy base material are adjacent one another are, because in the course of processing and/or when changing temperature, because of
For the significant difference (CTE-does not mates) of thermal coefficient of expansion between constituent components, may occur in which defect such as crackle, substrate camber, stripping
Broken etc. from, base material.
Because this change in size caused due to the high CTE of epoxy material, generation semiconductor base material, printed circuit board (PCB)
(PCB), encapsulation, the exploitation of OTFT (OTFT), flexible display base material etc. are restricted.Particularly recently half
In conductor and PCB industry, because epoxy resin has significantly high CTE compared with metal material/ceramic material, need high level
Design and Machining and the reliability of the assembly of future generation of integrated, miniaturization, flexible and high-performance etc. can be more difficult.In other words, exist
When manufacturing assembly, because under the processing temperature of assembly, the higher thermal expansion character of polymeric material, may occur in which defect,
And also limit manufacturing process.Can be a problem additionally, realize the design of assembly, processing characteristics and reliability.Therefore, in order to ensure electricity
The processing characteristics of sub-component and reliability, need the epoxy material with the thermal expansion characteristics such as dimensional stability of improvement.
Up to the present, (1) preparation and inorganic particle (inorganic filler) and/or the epoxy composite material of fabric are generally used
Method, or (2) design has the method for Novel ring oxygen compound of CTE of reduction, thus reduces the epoxy product of solidification
Thermal coefficient of expansion.
Epoxide with prepare as the inorganic particle of filler composite to improve thermal expansion characteristics in the case of,
Needing a large amount of diameter is the inorganic silicon dioxide granule of about 2-30 micron, obtains low CTE epoxy resin.But, because adding
Substantial amounts of inorganic particle, with processing characteristics and the temperature of performance that reduction occur.Specifically, because substantial amounts of inorganic particulate
Grain, mobility reduces, form hole etc. when filling narrow gap can be a problem.Additionally, because with the addition of inorganic particle, material
Viscosity can significantly increase.Additionally, because the semiconductor structure of miniaturization, the size of inorganic particle tends to reducing.But, using
In the case of diameter is less than or equal to the filler of 1 micron, the problem of the viscosity of increase can become more serious.Additionally, using
In the case of having the inorganic particle of bigger average diameter, resinous and inorganic particle compositions is not suitably filled with entering
The probability of the assembly applied increases.On the other hand, using containing organic resin and the situation of compositions of the fiber as filler
Under, CTE can be significantly reduced, but compared with silicon etc., the CTE of composite is the highest.
Because the restriction of the composite technology of current epoxy resin described above, epoxy resin is highly integrated, high
Application in performance electronic building brick such as generation semiconductor and PCB etc. is restricted.Accordingly, it would be desirable to exploitation has the heat of improvement
The lowest CTE of swelling properties and the epoxy composite material of high glass-transition temperature, solve problem, such as in existing thermosetting
Property polymer composites in high CTE and the not enough thermostability caused by the high CTE of composite and processing characteristics.
Therefore, the present inventor submit to korean patent application the 2012-93320th in, disclose have resistance to
The epoxide with alkoxysilyl of hot such as low thermal coefficient of expansion and high glass-transition temperature.But,
When epoxide is only made up of the alkoxysilyl that reactivity is the highest, during preparing composite, ring
The viscosity of oxygen compound can increase sharply.Accordingly, it would be desirable to exploitation epoxide, wherein can be efficiently controlled in and prepare composite wood
During material, viscosity increases sharply.
Summary of the invention
Technical problem
An aspect of of the present present invention may be provided in and presents the novel epoxide improving thermostability in composite, and
Comprise the mixture of described epoxide.
An aspect of of the present present invention may be provided in the novel epoxide presenting excellent processability in curing reaction, with
And comprise the mixture of described epoxide.
An aspect of of the present present invention may be provided in and presents the novel epoxide improving fragility in composite, and bag
Mixture containing described epoxide.
An aspect of of the present present invention may be provided in the novel epoxide presenting excellent flame character in cured product, with
And comprise the mixture of described epoxide.
An aspect of of the present present invention can provide preparation to present the novel epoxide improving thermostability in the composite
Method.
An aspect of of the present present invention can provide preparation to present the novel epoxy compound of excellent processability in curing reaction
The method of thing.
An aspect of of the present present invention can provide preparation to present the novel epoxy compound improving brittleness in the composite
The method of thing.
An aspect of of the present present invention can provide preparation to present the novel epoxide of excellent flame retardancy in cured product
Method.
An aspect of of the present present invention can provide compositions (hereinafter referred to as " epoxy composite), and described compositions is included in compound
Material presents the novel epoxide improving thermostability.
An aspect of of the present present invention may be provided in the epoxy composite in curing reaction with excellent processability.
An aspect of of the present present invention may be provided in and presents the epoxy composite improving brittleness in composite.
An aspect of of the present present invention may be provided in the epoxy composite in cured product with excellent flame character.
An aspect of of the present present invention may be provided in the cured product of the epoxy composite provided in the present invention.
An aspect of of the present present invention may be provided in the application of the epoxy composite provided in the present invention.
Technical scheme
According to first aspect, it is provided that epoxide, it comprises i) selected from the ring with following general formula E 1 and E2 in core
At least two epoxide group of oxygen groups；Ii) selected from least one alkoxysilyl of lower group: following formula A1 to A5；
And iii) selected from least one non-reacted silicyl, thiazolinyl or a combination thereof of lower group: following formula A6 to A10.
[general formula E 1]
[general formula E 2]
[formula A1]
-CRbRc-CHRa-CH2-SiR1R2R3
[formula A2]
-O-(CH2)m+2-SiR1R2R3
[formula A3]
-O-CONH(CH2)m-SiR1R2R3
[formula A4]
-(CH2)m+2-SiR1R2R3
[formula A5]
-CONH(CH2)m-SiR1R2R3
(in formula A1, Ra,RbAnd RcIt is H or the alkyl with 1 to 6 carbon atoms independently, and at above-mentioned formula A1
In A5, R1To R3In at least one be the alkoxyl with 1 to 6 carbon atoms, remaining R1To R3It is that there are 1 to 10
The alkyl of carbon atom, wherein alkyl and alkoxyl can be straight or branched, can be ring-type or acyclic, and can be with or without
N, O, S, or P hetero atom, and m is the integer of 1 to 10.)
[formula A6]
-CRbRc-CHRa-CH2-SiR4R5R6
[formula A7]
-O-(CH2)m+2-SiR4R5R6
[formula A8]
-O-CONH(CH2)m-SiR4R5R6
[formula A9]
-(CH2)m+2-SiR4R5R6
[formula A10]
-CONH(CH2)m-SiR4R5R6
(in above-mentioned formula A6, Ra,RbAnd RcIt is H or the alkyl with 1 to 6 carbon atoms independently, at above-mentioned formula
In A6 to A10, R4To R6It is that there is the aliphatic of 1 to 20 carbon atoms, the alicyclic or non-reacted group of aryl moieties,
Wherein said non-reacted group can be straight or branched, can be ring-type or acyclic, and can be with or without N, O, S, or P
Hetero atom, and m is the integer of 1 to 10.)
According to second aspect, in the first aspect, described thiazolinyl is selected from lower group: following formula A11 to A13.
[formula A11]
-CRbRc-CRa=CH2
[formula A12]
-O-(CH2)m-CH=CH2
[formula A13]
-(CH2)m-CH=CH2
(in formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein alkyl can be straight
Chain or side chain, can be ring-type or acyclic, and can be with or without the m in N, O, S, or P hetero atom, and formula A12 and A13
It it is the integer of 1 to 10.)
According to the third aspect, in the first aspect, described core is selected from lower group: following formula AC to OC.
(in above-mentioned general formula D C, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
At above-mentioned formula HC, J is to be directly connected to group ,-CH2-, or
(Rx is H or C1-C3Alkyl),
In above-mentioned formula IC, K is the one selected from lower group: following formula 1ac to 1fc,
In above-mentioned formula LC, L is
?In,
Ry is straight or branched C1-C10 alkyl,
In above-mentioned formula M C, M is CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, or
And R is H or C1-C3Alkyl,
In above-mentioned formula IC, when K is 1ac to 1ec, n is the integer of 3 or bigger, and when K is 1fc, and n is 2 or more
Big integer,
In above-mentioned formula JC, n is the integer of two or more,
In above-mentioned formula KC, n is the integer of 0 or bigger, at above-mentioned formula LC, when L isTime, n is the integer of 3 or bigger, and
When L isTime, n is the integer of two or more,
According to fourth aspect, in a third aspect, when selected from above-mentioned formula AC to HC and the same type of formula M C to OC
Core when being two or more, the core of above-mentioned formula AC to HC can be connected by following linking group LG1, and above-mentioned formula
The core of MC to OC can be connected by following linking group LG2.
[formula LG1]
[formula LG2]
According to the 5th aspect, in the first aspect, described epoxide can arbitrary by following formula AF to OF
Plant and represent.
(at least two in the substituent A of above-mentioned formula AF to FF is selected from following general formula E 1 and E2, in substituent A
At least one is selected from lower group: following formula A1 to A3, and remaining substituent A can be independently selected from lower group: above-mentioned formula A6
To A8, formula A11, formula A12, and hydrogen,
At least two in the substituent A of above-mentioned formula GF to LF can be represented, in substituent A by following general formula E 1
At least one can be represented by following formula A2 or formula A3, and remaining substituent A can be independently selected from lower group: following logical
Formula A7, following formula A8, following formula A12, and hydrogen, and
At least two in the substituent A of above-mentioned formula M F to OF can be represented, in substituent A by following general formula E 2
At least one is selected from following formula A4 and A5, and remaining substituent A can be independently selected from lower group: following formula A9, following
Formula A10, following formula A13, and hydrogen,
In above-mentioned general formula D F, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-
In above-mentioned formula HF, J is to be directly connected to
Group ,-CH2-, or
(Rx is H or C1-C3Alkyl),
In above-mentioned formula IF, K one in lower group: following formula 1A to 1F,
In above-mentioned formula LF, L is
AndIn, Ry is straight or branched C1-C10 alkyl,
In above-mentioned formula M F, M is CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, orAnd R is H or C1-C3Alkyl,
In above-mentioned formula IF, when K is 1A to 1E, n is the integer of 3 or bigger,
When K is 1F, n is the integer of two or more,
In above-mentioned formula JF, n is the integer of two or more,
In above-mentioned formula KF, n is the integer of 0 or bigger,
At above-mentioned formula LF, when L is
Time, n is the integer of 3 or bigger,
And when L is
Time, n is the integer of two or more, and
In above-mentioned formula LF, p is 1 or 2.
[general formula E 1]
[general formula E 2]
[formula A1]
-CRbRc-CHRa-CH2-SiR1R2R3
[formula A2]
-O-(CH2)m+2-SiR1R2R3
[formula A3]
-O-CONH(CH2)m-SiR1R2R3
[formula A4]
-(CH2)m+2-SiR1R2R3
[formula A5]
-CONH(CH2)m-SiR1R2R3
(in formula A1, Ra,RbAnd RcIt is H or the alkyl with 1 to 6 carbon atoms independently, and at above-mentioned formula A1
In A5, R1To R3In at least one be the alkoxyl with 1 to 6 carbon atoms, remaining R1To R3It is that there are 1 to 10
The alkyl of carbon atom, wherein alkyl and alkoxyl can be straight or branched, can be ring-type or acyclic, and can be with or without
N, O, S, or P hetero atom, and m is the integer of 1 to 10.)
[formula A6]
-CRbRc-CHRa-CH2-SiR4R5R6
[formula A7]
-O-(CH2)m+2-SiR4R5R6
[formula A8]
-O-CONH(CH2)m-SiR4R5R6
[formula A9]
-(CH2)m+2-SiR4R5R6
[formula A10]
-CONH(CH2)m-SiR4R5R6
(in above-mentioned formula A6, Ra,RbAnd RcIt is H or the alkyl with 1 to 6 carbon atoms independently, at above-mentioned formula
In A6 to A10, R4To R6It is that there is the aliphatic of 1 to 20 carbon atoms, the alicyclic or non-reacted group of aryl moieties,
Wherein said non-reacted group can be straight or branched, can be ring-type or acyclic, and can be with or without N, O, S, or P
Hetero atom, and m is the integer of 1 to 10.)
[formula A11]
-CRbRc-CRa=CH2
[formula A12]
-O-(CH2)m-CH=CH2
[formula A13]
-(CH2)m-CH=CH2
(in formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein alkyl can be straight
Chain or side chain, can be ring-type or acyclic, and can be with or without N, O, S, or P hetero atom, and in formula A12 and A13,
M is the integer of 1 to 10.)
According to the 6th aspect, in the first aspect, described epoxide can comprise i) at least two epoxy radicals in core
Group, it is represented by following general formula E 1
[general formula E 1]
I i) at least one alkoxysilyl, it is represented by following formula A1
[formula A1]
-CRbRc-CHRa-CH2-SiR1R2R3
(in formula A1, Ra,RbAnd RcIt is H or the alkyl with 1 to 6 carbon atoms independently, R1To R3In at least one
The individual alkoxyl being to have 1 to 6 carbon atoms, remaining R1To R3The alkyl with 1 to 10 carbon atoms, wherein alkyl and
Alkoxyl can be straight or branched, can be ring-type or acyclic, and can be with or without N, O, S, or P hetero atom, and m is
The integer of 1 to 10.)；And
Iii) at least one thiazolinyl, it is represented by following formula A11
[formula A11]
-CRbRc-CRa=CH2
(in formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein alkyl can be straight
Chain or side chain, can be ring-type or acyclic, and can be with or without N, O, S, or P hetero atom.)
According to the 7th aspect, in the first aspect, in the alkoxysilyl represented by above-mentioned formula A1 to A5
R1To R3In at least one can be the alkoxyl with 2 to 4 carbon atoms.
According to eighth aspect, in the first aspect, in the alkoxysilyl represented by above-mentioned formula A1 to A5
R1To R3It can be ethyoxyl.
According to the 9th aspect, when in the first aspect, the alkoxysilyl represented by above-mentioned formula A1 to A5
In whole R1To R3When being all methoxyl group, described epoxide can comprise at least one thiazolinyl.
According to the tenth aspect, providing the mixture of epoxide, it is arbitrary in comprising in terms of first aspect is to the 9th
Epoxide described in Xiang, wherein when epoxide comprises non-reacted silicyl, alkoxysilyl and non-
The ratio of reactive silicyl is 1:99 to 99:1.
According to the 11st aspect, preparation is provided to have the method for the epoxide of any one in following formula AF to OF,
Described method is included under conditions of there is platinum catalyst and optional solvent, and in following formula AS1 to OS1, any one is initial
The reaction of the alkoxy silane of material and following formula AS5, or parent material, there is the alkoxy silane of following formula AS5
Reaction with the non-reacted silane with following formula AS6.
[formula AS5]
HSiR1R2R3
(in above-mentioned formula AS5, R1To R3In at least one be C1-C6 alkoxyl, specifically ethyoxyl, remaining R1
To R3Be C1-C10 alkyl, wherein alkoxyl and alkyl can be straight or branched, can be ring-type or acyclic, and can have or not
There is N, O, S, or P hetero atom.)
[formula AS6]
HSiR4R5R6
(in above-mentioned formula AS6, R4To R6It is that there is the aliphatic of 1 to 20 carbon atoms, alicyclic or aryl moieties
Non-reacted group, the most non-reacted group can be straight or branched, can be ring-type or acyclic, and can have or do not have
There is N, O, S, or P hetero atom.)
(at least two in multiple substituent groups a1 of above-mentioned formula AS1 to FS1 can carry out table by following general formula E 1 or E2
Showing, at least two in multiple substituent groups a1 can be represented by following formula A11 or A12, and remaining substituent group a1 can be hydrogen,
At least two in substituent group a1 of above-mentioned formula GS1 to LS1 can be represented by following general formula E 1, substituent group a1
In at least two can be represented by following formula A12, remaining substituent group a1 can be hydrogen,
At least two in substituent group a1 of above-mentioned formula M S1 to OS1 can be represented by above-mentioned general formula E 2, and remaining takes
Can be represented by above-mentioned formula A13 for base a1,
In above-mentioned general formula D S1, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
In above-mentioned formula HS1, J is to be directly connected to group ,-CH2-, or
(Rx is H or C1-C3Alkyl),
In above-mentioned formula IS1, K is the one selected from lower group: following formula 1a1 to 1f1,
In above-mentioned formula LS1, L is
AndIn, Ry is straight or branched C1-C10 alkyl,
In above-mentioned formula M S1, M is CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, orAnd R is H or C1-C3Alkyl,
At above-mentioned formula IS1, when K is 1a1 to 1e1, n is the integer of 3 or bigger,
When K is 1f1, n is the integer of two or more,
In above-mentioned formula JS1, n is the integer of two or more,
In above-mentioned formula KS1, n is the integer of 0 or bigger,
In above-mentioned formula LS1, when L is
Time, n is the integer of 3 or bigger, and
When L is
Time, n is the integer of two or more,
In above-mentioned formula LS1, p is 1 or 2.
[general formula E 1]
[general formula E 2]
[formula A11]
-CRbRc-CRa=CH2
[formula A12]
-O-(CH2)m-CH=CH2
[formula A13]
-(CH2)m-CH=CH2
(in formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein alkyl can be straight
Chain or side chain, can be ring-type or acyclic, and can be with or without N, O, S, or P hetero atom, and in formula A12 and A13,
M is the integer of 1 to 10.)
(at least two in the substituent A of above-mentioned formula AF to FF can be represented by above-mentioned general formula E 1 or E2, substituent group
At least one in A is selected from lower group: following formula A1 to A2, and remaining substituent A can be independently selected from lower group: following logical
Formula A6, formula A7, formula A11, formula A12, and hydrogen,
At least two in the substituent A of above-mentioned formula GF to LF can be represented, in substituent A by following general formula E 1
At least one can be represented by following formula A2, and remaining substituent A can be independently selected from lower group: following formula A7 and
A12, and hydrogen,
At least two in the substituent A of above-mentioned formula M F to OF can be represented, in substituent A by following general formula E 2
At least one can be represented by following formula A4, and remaining substituent A can be independently selected from lower group: following formula A9 and
A13, and hydrogen,
In above-mentioned general formula D F, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,And
In above-mentioned formula HF, J is to be directly connected to group ,-CH2-, or
(Rx is H or C1-C3Alkyl),
In above-mentioned formula IF, K is the one selected from lower group: following formula 1A to 1F,
In above-mentioned formula LF, L is
And
In, Ry is straight or branched C1-C10 alkyl,
In above-mentioned formula M F, M is CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, orAnd R is H or C1-C3Alkyl,
In above-mentioned formula IF, when K is 1A to 1E, n is the integer of 3 or bigger,
When K is 1F, n is the integer of two or more,
In above-mentioned formula JF, n is the integer of two or more,
In above-mentioned formula KF, n is the integer of 0 or bigger,
At above-mentioned formula LF, when L is
Time, n be 3 or bigger whole
Number, and
When L is
Time, n is the integer of two or more, and
In above-mentioned formula LF, p is 1 or 2.
[general formula E 1]
[general formula E 2]
[formula A1]
-CRbRc-CHRa-CH2-SiR1R2R3
[formula A2]
-O-(CH2)m+2-SiR1R2R3
[formula A4]
-(CH2)m+2-SiR1R2R3
(in formula A1, Ra,RbAnd RcIt is H or the alkyl with 1 to 6 carbon atoms independently, and at above-mentioned formula A1,
In A2 and A4, R1To R3In at least one be the alkoxyl with 1 to 6 carbon atoms, remaining R1To R3It is to have 1 to 10
The alkyl of individual carbon atom, wherein alkyl and alkoxyl can be straight or branched, can be ring-type or acyclic, and can have or do not have
There is N, O, S, or P hetero atom, and m is the integer of 1 to 10.)
[formula A6]
-CRbRc-CHRa-CH2-SiR4R5R6
[formula A7]
-O-(CH2)m+2-SiR4R5R6
[formula A9]
-(CH2)m+2-SiR4R5R6
(in above-mentioned formula A6, Ra,RbAnd RcIt is H or the alkyl with 1 to 6 carbon atoms independently, at above-mentioned formula
In A6, A7 and A9, R4To R6It is that there is the aliphatic of 1 to 20 carbon atoms, the alicyclic or non-reacted base of aryl moieties
Group, wherein said non-reacted group can be straight or branched, can be ring-type or acyclic, and can with or without N, O, S,
Or P hetero atom, and m is the integer of 1 to 10.)
[formula A11]
-CRbRc-CRa=CH2
[formula A12]
-O-(CH2)m-CH=CH2
[formula A13]
-(CH2)m-CH=CH2
(in formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein alkyl can be straight
Chain or side chain, can be ring-type or acyclic, and can be with or without N, O, S, or P hetero atom, and in formula A12 and A13,
M is the integer of 1 to 10.)
According to the 12nd aspect, in the 11st aspect, the method for epoxide is prepared in offer, wherein parent material and
The alkoxy silane with above-mentioned formula AS5 reacts to each other, thus relative to 1 equivalent thiazolinyl of parent material, has above-mentioned logical
The alkoxy silane of formula AS5 can be within the scope of 0.1 equivalent to 5 equivalents.
According to the 13rd aspect, in the 11st aspect, the method for epoxide is prepared in offer, wherein above-mentioned when having
Whole R of the alkoxy silane of formula AS51To R3When being methoxyl group, parent material and the alkoxyl silicone with above-mentioned formula AS5
Alkane reacts to each other, thus relative to 1 equivalent thiazolinyl of parent material, the alkoxy silane with above-mentioned formula AS5 can be greatly
In or equal to 0.1 equivalent and less than within the scope of 1 equivalent.
According to fourteenth aspect, in the first aspect, preparation is provided to have the epoxy of any one in following formula AF to OF
The method of compound, under conditions of described method is included in optional solvent existence, has appointing in above-mentioned formula AS2 to OS2
A kind of parent material and there is the reaction of alkoxy silane of following formula AS3, or parent material, there is following formula
The alkoxy silane of AS3, and there is the reaction of the non-reacted silane of following formula AS4.
[formula AS3]
OCN-(CH2)m-SiR1R2R3
(in above-mentioned formula AS3, R1To R3In at least one be C1-C6 alkoxyl, specifically ethyoxyl, remaining R1
To R3Be C1-C10 alkyl, wherein alkoxyl and alkyl can be straight or branched, can be ring-type or acyclic, and can have or not
There is N, O, S, or P hetero atom.M is the integer of 1 to 10, the integer of specifically 3 to 6.)
[formula AS4]
OCN-(CH2)m-SiR4R5R6
(in above-mentioned formula AS4, R4To R6It is that there is the aliphatic of 1 to 20 carbon atoms, alicyclic or aryl moieties
Non-reacted group, the most non-reacted group can be straight or branched, can be ring-type or acyclic, and can have or do not have
There is N, O, S, or P hetero atom, and m is the integer of 1 to 10, the integer of specifically 3 to 6.)
(at least two in substituent group a2 of above-mentioned formula AS2 to FS2 can be represented by following general formula E 2, substituent group
At least two in a2 can be hydroxyl, and remaining substituent group a2 can be independently selected from lower group: hydrogen and following formula A11,
At least two in substituent group a2 of above-mentioned formula GS2 to LS2 can be represented by above-mentioned general formula E 1, substituent group a2
In at least two can be hydroxyl, remaining substituent group a2 can be hydrogen,
At least two in substituent group a2 of above-mentioned formula M S2 to OS2 can be represented by above-mentioned general formula E 2, and remaining takes
Can be hydrogen for base a2,
In above-mentioned general formula D S2, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
In above-mentioned formula HS2, J is to be directly connected to group ,-CH2-, or
(Rx is H or C1-C3Alkyl),
In above-mentioned formula IS2, K is the one selected from lower group: following formula 1a2 to 1f2,
In above-mentioned formula LS2, L is
?In, Ry is straight or branched C1-C10 alkyl,
In above-mentioned formula M S2, M is CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, or
And R is H or C1-C3Alkyl,
In above-mentioned formula IS2, when K is 2a to 2e, n is the integer of 3 or bigger,
When K is 2f, n is the integer of two or more,
In above-mentioned formula JS2, n is the integer of two or more,
In above-mentioned formula KS2, n is the integer of 0 or bigger,
In above-mentioned formula LS2, when L is
Time,
N is the integer of 3 or bigger,
And
When L is
Time, n is the integer of two or more, and
In above-mentioned formula LS2, p is 1 or 2.)
[general formula E 1]
[general formula E 2]
[formula A11]
-CRbRc-CRa=CH2
(in formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein alkyl can be straight chain
Or side chain, can be ring-type or acyclic, and can be with or without N, O, S, or P hetero atom.)
(at least two in the substituent A of above-mentioned formula AF to FF can be represented, in substituent A by following general formula E 2
At least one can be represented by following formula A3, and remaining substituent A can be independently selected from lower group: above-mentioned formula A8,
Following formula A11, and hydrogen,
At least two in the substituent A of above-mentioned formula GF to LF can be represented, in substituent A by following general formula E 1
At least one can be represented by following formula A3, and remaining substituent A can independently selected from following formula A8 and hydrogen,
At least two in the substituent A of above-mentioned formula M F to OF can be represented, in substituent A by following general formula E 2
At least one can be represented by following formula A5, and remaining substituent A can independently selected from following formula A10 and hydrogen,
In above-mentioned general formula D F, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
In above-mentioned formula HF, J is to be directly connected to group ,-CH2-, or
(Rx is H or C1-C3Alkyl),
In above-mentioned formula IF, K is the one selected from lower group: following formula 1A to 1F,
In above-mentioned formula LF, L is
?In, Ry is straight or branched C1-C10 alkyl,
In above-mentioned formula M F, M is CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, or
And R is H or C1-C3Alkyl,
In above-mentioned formula IF, when K is 1A to 1E, n is the integer of 3 or bigger, and when K is 1F, n is two or more
Integer,
In above-mentioned formula JF, n is the integer of two or more,
In above-mentioned formula KF, n is the integer of 0 or bigger,
At above-mentioned formula LF, when L is
Time, n is the integer of 3 or bigger, and
When L is
Time, n is the integer of two or more, and
In above-mentioned formula LF, p is 1 or 2.
[general formula E 1]
[general formula E 2]
[formula A3]
-O-CONH(CH2)m-SiR1R2R3
[formula A5]
-CONH(CH2)m-SiR1R2R3
(in above-mentioned formula A3 and A5, R1To R3In at least one be the alkoxyl with 1 to 6 carbon atoms, and its
Remaining R1To R3Be the alkyl with 1 to 10 carbon atoms, wherein alkyl and alkoxyl can be straight or branched, can be ring-type or
Acyclic, and can be with or without N, O, S, or P hetero atom, and m is the integer of 1 to 10.)
[formula A8]
-O-CONH(CH2)m-SiR4R5R6
[formula A10]
-CONH(CH2)m-SiR4R5R6
(in above-mentioned formula A8 and A10, R4To R6It is that there is the aliphatic of 1 to 20 carbon atoms, alicyclic or aromatic series
Part non-reacted group, the most non-reacted group can be straight or branched, can be ring-type or acyclic, and can have or
Not there is N, O, S, or P hetero atom, and m is the integer of 1 to 10.)
[formula A11]
-CRbRc-CRa=CH2
(in formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein alkyl can be straight chain
Or side chain, can be ring-type or acyclic, and can be with or without N, O, S, or P hetero atom.)
According to the 15th aspect, in fourteenth aspect, the method for epoxide is prepared in offer, wherein parent material and
The alkoxy silane with above-mentioned formula AS3 reacts to each other, thus relative to 1 equivalent amino or hydroxyl of parent material, has
The alkoxy silane of above-mentioned formula AS3 can be within the scope of 0.1 equivalent to 5 equivalents.
According to the 16th aspect, in fourteenth aspect, the method for epoxide is prepared in offer, wherein above-mentioned when having
Whole R of the alkoxy silane of formula AS31To R3When being methoxyl group, parent material and the alkoxyl silicone with above-mentioned formula AS3
Alkane reacts to each other, thus relative to 1 equivalent amino or hydroxyl of parent material, the alkoxy silane with above-mentioned formula AS3 can
For more than or equal to 0.1 equivalent and less than within the scope of 1 equivalent.
According to the 17th aspect, it is provided that epoxy composite, it comprises according to any one of in terms of first aspect is to the 9th
Epoxide.
According to the 18th aspect, it is provided that epoxy composite, it comprises the epoxy mixture described in the tenth aspect.
According to the 19th aspect, in the 17th aspect and the 18th aspect, described epoxy composite also includes being selected from down
Group at least one epoxide: epoxide based on glycidyl ether, epoxide based on glycidyl,
Epoxide based on glycidyl amine, epoxide based on ethylene oxidic ester, rubber modified epoxy compound, based on
The epoxide of aliphatic polyglycidyl base and epoxide based on aliphatic glycidyl amine.
According to the 20th aspect, in the 19th aspect, described epoxide can comprise in nuclear structure bis-phenol, biphenyl, naphthalene,
Benzene, dihydroxy diphenyl sulfide (thiodiphenol), fluorenes, anthracene, isocyanuric acid ester, triphenyl methane, 1,1,2,2-tetraphenyl second
Alkane, tetraphenylmethane, 4,4'-MDA, amino-phenol, alicyclic compound, aliphatic compound or phenolic aldehyde are clear
Paint unit.
According to the 21st aspect, in the 19th aspect, count on the basis of the gross weight of epoxide, described epoxy composite
10 to 100 weight % can be comprised there is the epoxide of alkoxysilyl, and 0 weight % to 90 weight % is selected from lower group
At least one epoxide: epoxide based on glycidyl ether, epoxide based on glycidyl, base
In the epoxide of glycidyl amine, epoxide based on ethylene oxidic ester, rubber modified epoxy compound, based on fat
The epoxide of fat adoption glycidyl and epoxide based on aliphatic glycidyl amine.
According to the 22nd aspect, in the 17th aspect to the either side of the 21st aspect, epoxy composite also can comprise and is selected from
At least one filler of lower group: inorganic particle or fiber.
According to the 23rd aspect, in the 22nd aspect, described inorganic particle can be selected from least one of lower group: selected from lower group
At least one metal-oxide: silicon dioxide, zirconium oxide, titanium oxide, aluminium oxide, silicon nitride, aluminium nitride and silsesquioxane
(silsesquioxane)。
According to the 24th aspect, in the 22nd aspect, described fiber can be selected from least one of lower group: glass fibre and having
Organic fiber, described glass fibre is selected from E glass fibre, T glass fibre, S glass fibre, NE glass fibre, H glass fibre and stone
English glass fibre；And described organic fiber is fine selected from liquid crystalline polyester fiber, dacron fibre, full aromatics
Dimension, polybenzoxazole (polybenzoxazole) fiber, nylon fiber, PEN fiber, polypropylene fibre,
Polyether sulfone fiber, polyvinylidene fluoride fiber, polyethylene sulfide fiber and polyetheretherketonefiber fiber.
According to the 25th aspect, when comprising fiber in the 22nd aspect, epoxy composite also can comprise inorganic particle.
According to the 26th aspect, it is provided that electronic material, it comprises the 17th aspect to the epoxy according to any one of the 25th aspect
Compositions.
According to the 27th aspect, it is provided that base material, it comprises the 17th aspect to the epoxy combination according to any one of the 25th aspect
Thing.
According to the 28th aspect, it is provided that film, it comprises the 17th aspect to the epoxy composite according to any one of the 25th aspect.
According to the 29th aspect, it is provided that laminate, it is included in by the 17th aspect to the ring according to any one of the 25th aspect
The metal level on basal layer that oxygen compositions is formed.
According to the 30th aspect, it is provided that printed circuit board (PCB), it comprises the laminate described in the 29th aspect.
According to the 31st aspect, it is provided that semiconductor device, it comprises the printed circuit board (PCB) described in the 30th aspect.
According to the 32nd aspect, it is provided that semiconductor sealing material, it comprises the 17th aspect to according to any one of the 25th aspect
Epoxy composite.
According to the 33rd aspect, it is provided that semiconductor device, it comprises the semiconductor sealing material described in the 32nd aspect.
According to the 34th aspect, it is provided that adhesive, it comprises the 17th aspect to the epoxy group according to any one of the 25th aspect
Compound.
According to the 35th aspect, it is provided that paint, it comprises the 17th aspect to the epoxy combination according to any one of the 25th aspect
Thing.
According to the 36th aspect, it is provided that composite, it comprises the 17th aspect to the epoxy according to any one of the 25th aspect
Compositions.
According to the 37th aspect, it is provided that pre impregnated material (prepreg), it comprises the 13rd aspect to any one of the 25th aspect
Described epoxy composite.
According to the 38th aspect, providing laminate, wherein metal level is arranged on the pre impregnated material described in the 37th aspect.
According to the 39th aspect, provide the 17th aspect to the solidification product of the epoxy composite according to any one of the 25th aspect
Thing.
According to the 40th aspect, in the 39th aspect, the cured product of epoxy composite can have less than or equal to 60ppm/
DEG C thermal coefficient of expansion.
According to the 41st aspect, in the 39th aspect, the cured product of epoxy composite can have the vitrification higher than 100 DEG C
Transition temperature, or glass transition temperature can not be presented.
Beneficial effect
As it has been described above, according to the illustrative embodiments in the present invention, in composite and/or cured product, comprise
The epoxy composite of novel epoxide can present the thermostability of improvement, and such as epoxy composite material CTE declines and glass
Change transition temperature and increase (comprising without the effect observing glass transition temperature (hereinafter referred to as " without Tg's ")).This
Outward, because introducing alkoxysilyl, according to the cured product of the epoxy composite of the illustrative embodiments in the present invention
Excellent flame character can be provided.Additionally, according to the epoxy composite of the illustrative embodiments in the present invention in curing reaction
Excellent processability can be presented.Specifically, the viscosity in curing reaction can be controlled easily increase.In addition, epoxy composite
Cured product can present the fragility of improvement.
Additionally, since by the efficiency of the improvement of the chemical bond of epoxide, comprise according in the present invention is exemplary
The compositions of the epoxide of embodiment need not silane coupler, and according to related art, silane coupler is usual
In epoxy composite.
Accompanying drawing explanation
Figure 1A is the micro-image (100 times on the glass fiber compound material surface using the preparation of comparative synthetic example 1
Amplification)；
Figure 1B is micro-image (100 times of times magnifications on the glass fiber compound material surface using synthetic example 4 preparation
Number)；
Fig. 2 A is outward appearance (left side) and the micro-image of the glass fiber compound material with the preparation of comparative synthetic example 2
(the right, 100 times of amplifications), the internal break of its display glass fiber compound material；And
Fig. 2 B is that the glass fibre with the preparation of comparative synthetic example 2 for glass fiber compound material surface is combined
The outward appearance (left side) of material and micro-image (the right, 100 times of amplifications).
Invention preferred forms
The present invention provides novel epoxide, when preparing composite by cured epoxy compositions, described
Epoxide has the heat-resisting character of improvement, has low thermal coefficient of expansion (CTE), and high Tg (comprising without Tg's) specifically
And/or the excellent flame character in cured product, the fragility of the improvement in cured product, and/or curing reaction character, example
As viscosity increases controllability, the method also providing for preparing described epoxide, comprise the epoxy combination of described epoxide
Thing and cured product, and application.
In the present invention, " composite " refers to comprise epoxide and the combination of filler (fiber and/or inorganic particle)
The cured product of thing.In the present invention, " cured product " is commonly referred to as the cured product of the compositions comprising epoxide,
The cured product of such as compositions comprises selected from least one of lower group: filler, optional and extra firming agent, optional consolidating
Change catalyst and other additive, and epoxide and firming agent.Additionally, cured product can include partially cured product.
Composite will be referred to as with inorganic particle and/or fibre-reinforced cured product typically, since known, so the containing of cured product
Justice is more broader than the implication of composite.It is contemplated, however, that with inorganic particle and/or fibre-reinforced cured product with compound
Material has identical implication.
Novel epoxide according to illustrative embodiments can have reactive group and non-reacted group.Cause
This, when forming composite in the curing process, carry out cross-linking reaction by the reaction of epoxide group Yu firming agent, reaction
Property group can be connected with filler (fiber and/or inorganic particle) formation interface, surface.Therefore, epoxy composite material system can present
The best chemical bonding is formed, and this obtains low CTE and glass transition temperature increases (comprising without Tg's).Cause
This, can improve dimensional stability.In addition, independent silane coupler can be need not.In addition, comprise according to illustrative embodiments
The cured product of epoxide can present excellent flame character.In addition, in cured product, non-reacted group can conduct
The free end of suspended portion exists, and this causes viscosity and/or the fragility of final cured product improving in solidification process.Reaction
Property group can be alkoxysilyl specifically, and non-reacted group can be such as aIkylsilyl groups.
1. epoxide
Novel epoxide according to the illustrative embodiments in the present invention can have at least two ring in core
Oxygen groups；At least one alkoxysilyl；With at least one non-reacted silicyl, thiazolinyl or a combination thereof.
Epoxide group can be independently selected from general formula E 1 and E2.
[general formula E 1]
[general formula E 2]
Alkoxysilyl can be selected from least one of lower group: formula A1 to A5.
[formula A1]
-CRbRc-CHRa-CH2-SiR1R2R3
[formula A2]
-O-(CH2)m+2-SiR1R2R3
[formula A3]
-O-CONH(CH2)m-SiR1R2R3
[formula A4]
-(CH2)m+2-SiR1R2R3
[formula A5]
-CONH(CH2)m-SiR1R2R3
In formula A1, Ra,Rb, and RCIt is hydrogen (H) or the alkyl with 1 to 6 carbon atoms independently of one another.At formula
In A1 to A5, R1To R3In at least one be the alkoxyl with 1 to 6 carbon atoms.Remaining is that to have 1 to 10 carbon former
The alkyl of son.Each Wei straight or branched in alkyl and alkoxyl, can be ring-type or acyclic, and can have or do not have
There is N, O, S, or P hetero atom.In addition, m is the integer of 1 to 10.
Non-reacted silicyl can be selected from least one of lower group: formula A6 to A10.
Under the alkoxysilyl and non-reacted silicyl ratio of preferred scope, according to exemplary embodiment party
In the composite of formula, present the heat-resisting character (CTE declines and/or glass transition temperature increases) of improvement, increase viscosity and increase
Adding effect and fragility and decline the controllability of effect, within the scope of preferably, these physical propertys can be it is furthermore preferred that and preferred model
Enclose and be applicable to wherein epoxy composite material and be used as the situation of semiconductor packages.
[formula A6]
-CRbRc-CHRa-CH2-SiR4R5R6
[formula A7]
-O-(CH2)m+2-SiR4R5R6
[formula A8]
-O-CONH(CH2)m-SiR4R5R6
[formula A9]
-(CH2)m+2-SiR4R5R6
[formula A10]
-CONH(CH2)m-SiR4R5R6
In formula A6, Ra,Rb, and RCIt is hydrogen (H) or the alkyl with 1 to 6 carbon atoms independently of one another.At formula
In A6 to A10, R4To R6It is that there is the aliphatic of 1 to 20 carbon atoms, the alicyclic or non-reacted group of aryl moieties.
Non-reacted group can be straight or branched, can be ring-type or acyclic, and can be with or without N, O, S, or P hetero atom.
In addition, m is the integer of 1 to 10.
Meanwhile, thiazolinyl is selected from lower group: formula A11 to A13.
[formula A11]
-CRbRc-CRa=CH2
[formula A12]
-O-(CH2)m-CH=CH2
[formula A13]
-(CH2)m-CH=CH2
In formula A11, Ra,Rb, and RCIt is hydrogen (H) or the alkyl with 1 to 6 carbon atoms independently of one another.Alkyl can
For straight or branched, can be ring-type or acyclic, and can be with or without N, O, S, or P hetero atom.At formula A12 and A13
In, m is the integer of 1 to 10.
According to illustrative embodiments, thiazolinyl comprises can be by removing single hydrogen atom from olefin(e) compound or derivatives thereof
And all chemical groups obtained, including pi-allyl, cyclobutenyl, pentenyl etc., and these terms are used interchangeably.
Nuclear structure can be bis-phenol, biphenyl, naphthalene, benzene, dihydroxy diphenyl sulfide, fluorenes, tetraphenyl ethane, tetraphenylmethane, two
Diaminodiphenylmethane, alicyclic compound, aliphatic compound or novolaks unit etc..
Specifically, core is aromatic series core, and can be selected from least one of lower group: formula AC to OC.According to exemplary
Embodiment, core is understood as comprising formula AC to HC and the structure of formula M C to OC and the repetitive of formula IC to LC.
In general formula D C, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
In formula HC, J is to be directly connected to group ,-CH2-orWherein Rx is hydrogen (H) or C1-C3 alkane
Base.
In formula IC, K is selected from least one of lower group: formula 1ac to 1fc:
In formula LC, L isAnd,In, Ry is straight or branched C1-C10 alkyl.
In formula M C, M is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, orR is hydrogen (H) or C1-C3 alkyl.
In formula IC, when K is formula 1ac to 1ec, n is the integer of 3 or bigger, when K is formula 1fc, n be 2 or
Bigger integer.
In formula JC, n is the integer of two or more.
In formula KC, n is the integer of 0 or bigger.
In formula LC, when L is
Time, n is the integer of 3 or bigger, when L isTime, n is the integer of two or more.
In formula IC to LC, the maximum of n is 1,000.
In addition, in epoxide, when the core with formula AC to HC and formula M C to OC is two or more
(in this case, core is same type, and when being two or more according to the core of illustrative embodiments, above-mentioned
It is applicable to this most in the same manner), core can pass through linking group (LG) and connect.According to circumstances need, 1 can be connected extraly and arrive
1,000 nuclear structures.Specifically, the core of formula AC to HC can be connected by the linking group of formula LG1, formula M C to OC
Core can be connected by the linking group of formula LG2.
[formula LG1]
[formula LG2]
Specifically, the novel epoxide according to the illustrative embodiments in the present invention can be that formula AF arrives
OF。
At least two in the substituent A of formula AF to FF is selected from general formula E 1 and E2, and at least one in substituent A can
Selected from lower group: following formula A1 to A3, and remaining substituent A can be independently selected from lower group: formula A6 to A8, formula A11, logical
Formula A12, and hydrogen (H).
At least two in the substituent A of formula GF to LF can be general formula E 1, at least one Wei the formula in substituent A
A2 or A3, and remaining substituent A can be independently selected from lower group: formula A7, A8, and A12, and hydrogen (H).
At least two in the substituent A of formula M F to OF can be general formula E 2, and at least one in substituent A is selected from leading to
Formula A4 and A5, and remaining substituent A can be independently selected from lower group: formula A9, A10, and A13, and hydrogen (H).
In general formula D F, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
In formula HF, J is to be directly connected to group ,-CH2-orWherein Rx is hydrogen (H) or C1-C3 alkane
Base.
In formula IF, K is selected from least one of lower group: formula 1A to 1F:
In formula LF, L isAnd,
?In, Ry is straight or branched C1-C10 alkyl.
In formula M F, M is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, orR is hydrogen (H) or C1-C3 alkyl.
In formula IF, when K is formula 1A to 1E, n is the integer of 3 or bigger, and when K is formula 1F, n is 2 or more
Big integer.
In formula JF, n is the integer of two or more.
In formula KF, n is the integer of 0 or bigger.
In formula LF, when L is
Time, n is the integer of 3 or bigger, when L isTime, n is the integer of two or more.
In formula LF, p is 1 or 2.In formula IF to LF, the maximum of n is 1,000.
[general formula E 1]
[general formula E 2]
[formula A1]
-CRbRc-CHRa-CH2-SiR1R2R3
[formula A2]
-O-(CH2)m+2-SiR1R2R3
[formula A3]
-O-CONH(CH2)m-SiR1R2R3
[formula A4]
-(CH2)m+2-SiR1R2R3
[formula A5]
-CONH(CH2)m-SiR1R2R3
In formula A1, Ra,Rb, and RCIt is hydrogen (H) or the alkyl with 1 to 6 carbon atoms independently of one another.At formula
In A1 to A5, R1To R3In at least one be the alkoxyl with 1 to 6 carbon atoms.Remaining is that to have 1 to 10 carbon former
The alkyl of son.Each Wei straight or branched in alkyl and alkoxyl, can be ring-type or acyclic, and can have or do not have
There is N, O, S, or P hetero atom.In addition, m is the integer of 1 to 10.
[formula A6]
-CRbRc-CHRa-CH2-SiR4R5R6
[formula A7]
-O-(CH2)m+2-SiR4R5R6
[formula A8]
-O-CONH(CH2)m-SiR4R5R6
[formula A9]
-(CH2)m+2-SiR4R5R6
[formula A10]
-CONH(CH2)m-SiR4R5R6
In formula A6, Ra,Rb,And RCIt is hydrogen (H) or the alkyl with 1 to 6 carbon atoms independently of one another.At formula
In A6 to A10, R4To R6It is that there is the aliphatic of 1 to 20 carbon atoms, the alicyclic or non-reacted group of aryl moieties.
Non-reacted group can be straight or branched, can be ring-type or acyclic, and can be with or without N, O, S, or P hetero atom.
In addition, m is the integer of 1 to 10.
[formula A11]
-CRbRc-CRa=CH2
[formula A12]
-O-(CH2)m-CH=CH2
[formula A13]
-(CH2)m-CH=CH2
In formula A11, Ra,Rb,And RCIt is hydrogen (H) or the alkyl with 1 to 6 carbon atoms independently of one another.Alkyl can
For straight or branched, can be ring-type or acyclic, and can be with or without N, O, S, or P hetero atom.At formula A12 and A13
In, m is the integer of 1 to 10.
Described epoxide can be epoxide, and it such as has (i) at least two epoxide group in core, and it leads to
Cross general formula E 1 to represent
[general formula E 1]
Ii) at least one alkoxysilyl, it is represented by formula A1:
[formula A1]
-CRbRc-CHRa-CH2-SiR1R2R3
In formula A1, Ra,Rb,And RCIt is hydrogen (H) or the alkyl with 1 to 6 carbon atoms independently of one another.The most extremely
A few alkoxyl being to have 1 to 6 carbon atoms.Remaining is the alkyl with 1 to 10 carbon atoms.Alkyl and alkoxyl
In each Wei straight or branched, can be ring-type or acyclic, and can be with or without N, O, S, or P hetero atom.This
Outward, m is the integer of 1 to 10；And
(iii) at least one thiazolinyl, it is represented by formula A11:
[formula A11]
-CRbRc-CRa=CH2
In formula A11, Ra,Rb, and RCIt is hydrogen (H) or the alkyl with 1 to 6 carbon atoms independently of one another.Alkyl can
For straight or branched, can be ring-type or acyclic, and can be with or without N, O, S, or P hetero atom.
In epoxide, by the R of the alkoxysilyl that formula A1 to A5 represents1To R3In at least one
The individual alkoxyl being to have 2 to 4 carbon atoms, and in the alkoxysilyl represented by formula A1 to A5 preferably
Ground can be ethyoxyl.
Meanwhile, as R whole in the alkoxysilyl represented by formula A1 to A51To R3It it is all methoxyl group
Time, preferably comprise at least one thiazolinyl according to the epoxide of illustrative embodiments.When in alkoxysilyl
R1To R3When being entirely methoxyl group and do not comprise at least one thiazolinyl, the excessive reactivity of methoxysilyl, thus because
Increasing sharply of viscosity etc., it is difficult to control its reaction rate, and the fragility of the sample of solidification is too high thus is difficult to apply this material.
On the contrary, as R whole in alkoxysilyl1To R3It is all methoxyl group and when comprising at least one thiazolinyl, because consolidated structures
In there is thiazolinyl, reaction rate can be controlled, and the fragility of the sample of solidification can be reduced.
According to the illustrative embodiments in the present invention, also providing for epoxy mixture, it comprised according to showing in the present invention
The novel epoxide of example embodiment.
Comprising according in the mixture of the novel epoxide of illustrative embodiments, when novel epoxy compound
When thing comprises non-reacted silicyl, the ratio of alkoxysilyl and non-reacted silicyl is 1:99 to 99:1,
And may preferably be 5:95 to 95:5.When the ratio of alkoxysilyl and non-reacted silicyl is less than 1:99, alkane
Epoxide silicyl concentration is too low, thus cannot ensure the physical property of adequate level.When alkoxysilyl and non-reaction
Property silicyl ratio more than 99:1 time, non-reacted silicyl concentration is too low, thus does not substantially reduce brittleness.
In comprising the mixture of epoxide of novelty, the ratio of epoxide group and alkoxysilyl can be 10:1 to 1:
10.When the ratio of epoxide group and alkoxysilyl is less than 1:10, the crosslink density of the epoxy product of solidification can reduce,
Thus cause its physical property to be deteriorated.When the ratio of epoxide group and alkoxysilyl is less than 10:1, alcoxyl can be reduced
The improved heat resistance effect of base silicyl.Additionally, in comprising the mixture of epoxide of novelty, alkoxy silicane
The ratio of base and non-reacted silicyl is 1:99 to 99:1, and may preferably be 5:95 to 95:5, epoxide group and alcoxyl
The ratio of base silicyl is 10:1 to 1:10, and can be such as 1:1 to 5:1.
Additionally, as described below according in the epoxy composite of the illustrative embodiments in the present invention, alkoxyl first
The ratio of silylation and the ratio of non-reacted silicyl and/or epoxide group and alkoxysilyl preferably with as above
Described is identical.Therefore, the epoxide comprised in epoxy composite as described below can be epoxidation as above
Compound.
Meanwhile, when comprising thiazolinyl according to the epoxide of illustrative embodiments, relative to 1 equivalent parent material
When thiazolinyl uses the alkoxy silane that 0.1 to 5 equivalents have formula AS5, parent material and the alkoxy silane with formula AS5
Between reaction be preferred.Have formula AS5's when using relative to the thiazolinyl of 1 equivalent parent material less than 0.1 equivalent
First silicon when alkoxy silane reacts, in the reaction rate of alkoxysilyl and final epoxy composite structures
Alkylation degree can significantly reduce.When using the alkane more than 5 equivalents with formula AS5 relative to the thiazolinyl of 1 equivalent parent material
When TMOS reacts, the unreacted alkoxysilyl concentration being present in excess can be dramatically increased.
Additionally, specifically, as whole R of the alkoxy silane with formula AS51To R3When being methoxyl group, Qi Zhongxiang
Thiazolinyl use for 1 equivalent parent material is more than or equal to 0.1 equivalent and has the alkoxyl silicone of formula AS5 less than 1 equivalent
The reaction of alkane is preferred.When using the alkane less than 0.1 equivalent with formula AS5 relative to the thiazolinyl of 1 equivalent parent material
Monosilane when TMOS reacts, in the reaction rate of methoxysilyl and final epoxy composite structures
Base degree can significantly reduce.When using the alcoxyl more than 5 equivalents with formula AS5 relative to the thiazolinyl of 1 equivalent parent material
When base silane reacts, the concentration of the methoxysilyl can being significantly increased in final epoxy composite structures.
Such as, in the epoxide that preparation is novel, because not reacting and/or incomplete reaction, according to the present invention
In the novel epoxide of illustrative embodiments can realize the state with mixture to obtain non-reacted initial material
Such as, material and reactive byproducts (only have epoxide group and the compound of alkoxysilyl or only have epoxide group
Compound with non-reacted silicyl), described by-product is unsatisfactory for being determined according to the illustrative embodiments in the present invention
The definition of the epoxide of justice, as hereafter institute is described in more detail.In the whole mixt of epoxide, alkoxyl first
The ratio of silylation and the ratio of non-reacted silicyl and/or epoxide group and alkoxysilyl can be described above
Scope, and the mixture of epoxide self can be used for epoxy composite as described below.
In the present invention, " alkoxyl " refers to monoradical OR (R is alkyl), and it can be straight or branched.
In the present invention, " alkyl " refers to monovalent hydrocarbon group, and it can be straight or branched.
When there is multiple substituent group in above-mentioned or following formula, each substituent group can be selected independently.Such as, when
At least two in the substituent A of formula AF to FF is when formula A1 to A3, and each in multiple substituent A can be the most only
On the spot selected from formula A1 to A3.Similarly, when all A are formula A2, the R of formula A21To R3May be the same or different.
Additionally, in comprising the composite of compositions of epoxide, according to the exemplary embodiment party in the present invention
The epoxide of formula can present low CTE and high glass-transition temperature or without Tg's.In addition, non-reacted silicyl and
Thiazolinyl can be not involved in extra chemical bonding, and can exist as the suspended portion on curable epoxide product cross-linked network, this because of
This causes viscosity and/or the fragility of final cured product improving in solidification process.
2. the method preparing epoxide
The epoxide with formula AF to OF according to the illustrative embodiments in the present invention can pass through following institute
The two kinds of methods stated synthesize.
That is, can be synthesized by following method according to the epoxide of illustrative embodiments: the hydrosilanes of double bond
Change method i.e. has the alkoxysilyl of the epoxide of epoxide group and thiazolinyl and non-reacted silylanizing
(method 1), or the reaction of hydroxyl or amido and isocynate silane coupling agent i.e. has the epoxide of hydroxyl and/or amido
Silylanizing (method 2).
(1) method 1
Such as, as mentioned above, it is necessary, manufactured by following according to the epoxide of illustrative embodiments: parent material is (
There is the epoxide of epoxide group and thiazolinyl) the alkoxysilyl of thiazolinyl and non-reacted silylanizing.
For convenience, hereinafter, the epoxide with epoxide group and thiazolinyl is referred to as parent material.Initial material
Material can specially have the compound of formula AS1 to OS1.
(parent material 1)
At least two in multiple substituent groups a1 of formula AS1 to FS1 is general formula E 1 or E2, at least two in substituent group a1
Individual is formula A11 or A12, and remaining substituent group a1 can be hydrogen (H).
At least two in multiple substituent groups a1 of formula GS1 to LS1 is general formula E 1, and at least two in substituent group a1 is
Formula A12, and remaining substituent group a1 can be hydrogen (H).
At least two in multiple substituent groups a1 of formula M S1 to OS1 is general formula E 2, and remaining substituent group a1 can be logical
Formula A13.
In general formula D S1, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
In formula HS1, J is to be directly connected to group ,-CH2-orAnd Rx is hydrogen (H) or C1-C3 alkane
Base.
In formula IS1, K is selected from least one of lower group: formula 1a1 to 1f1.
In formula LS1, L isWith
And,In, Ry is straight or branched C1-C10 alkyl.
In formula M S1, M is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, orR is hydrogen (H) or C1-C3 alkyl.
In formula IS1, when K is formula 1a1 to 1e1, n is the integer of 3 or bigger, and when K is formula 1f1, n is 2
Or bigger integer.
In formula JS1, n is the integer of two or more.
In formula KS1, n is the integer of 0 or bigger.
In formula LS1, when L is
Time, n is the integer of 3 or bigger, when L isTime, n is the integer of two or more.
In formula LS1, p is 1 or 2.In formula IS1 to LS1, the maximum of n is 1,000.
Specifically, under conditions of there is platinum catalyst and optional solvent, carry out the alcoxyl of the thiazolinyl of parent material
Base silylanizing and non-reacted silylanizing, thus obtain according to the illustrative embodiments in the present invention have to
Few two epoxide groups, at least one alkoxysilyl and at least one non-reacted functional group (the most non-reaction
Property silicyl and thiazolinyl) epoxide.
Anti-because of carry out between the thiazolinyl of parent material and the alkoxy silane with formula AS5 according to stoichiometry
Should, it is contemplated that to stoichiometry, use 0.1 to 5 equivalent alkoxy silanes relative to the thiazolinyl of 1 equivalent parent material, enter
Reaction between start of line material and the alkoxy silane with formula AS5.
Specifically, as whole R of the alkoxy silane with formula AS51To R3When being methoxyl group, wherein relative to 1
It is anti-that the thiazolinyl of equivalent parent material uses more than or equal to 0.1 equivalent and the alkoxy silane less than 1 equivalent with formula AS5
Should be preferred.In the case of being used below the alkoxy silane of concentration range, the reaction rate of methoxysilyl
Can be too low with silylanizing degree in final epoxy composite structures.In the feelings using the alkoxy silane more than concentration range
Under condition, the methoxysilyl concentration in final epoxy composite structures can be too high.
[formula AS5]
HSiR1R2R3
In formula AS5, R1To R3In at least one be C1 to C6 alkoxyl, preferably ethyoxyl, remaining R1Arrive
R3Being C1 to C10 alkyl, described alkoxyl and alkyl can be straight or branched, can be ring-type or acyclic, and can have or not
There is N, O, S, or P hetero atom.
Additionally, because carrying out the thiazolinyl of parent material according to stoichiometry and there is the non-reacted silane of formula AS6
Between reaction, it is contemplated that to stoichiometry, use 0.1 to 5 equivalents non-reacted relative to the thiazolinyl of 1 equivalent parent material
Silane, carries out the reaction between parent material and non-reacted silane.
[formula AS6]
HSiR4R5R6
In formula A6, R4To R6Be have the aliphatic of 1 to 20 carbon atoms, alicyclic or aryl moieties non-instead
Answering property group, non-reacted group can be straight or branched, can be ring-type or acyclic, and can with or without N, O, S, or
P hetero atom.
Reaction between parent material, alkoxy silane and non-reacted silane can comprise (1) parent material and alkoxyl
Silane and the reaction of non-reacted silane, comprise (2) parent material and the reaction of alkoxy silane simultaneously and reaction subsequently is produced
Thing reacts with the original position (in-situ) of non-reacted silane.
Parent material and the reaction temperature of alkoxy silane and response time can be depending on the structure of reaction material and change,
Such as reaction can carried out 1 hour to 72 hours at a temperature of-20 DEG C to 120 DEG C.By at the reaction temperatures, reaction is entered
In the row response time, required reaction can be completed.
Described platinum catalyst can be such as but not limited to PtO2Or chloroplatinic acid (H2PtCl6).In view of reaction efficiency, phase
For the thiazolinyl of the parent material of 1 equivalent, preferably use 1x10-4Platinum catalyst to 0.05 equivalent.
According to circumstances need, optionally use solvent.Such as, at the reaction temperatures the viscosity of reaction material be suitable for into
In the case of row reaction is without using single solvent, then can not use solvent.That is, low to making when reaction material viscosity
When obtaining the mixing of reaction material and stir the carrying out that can smooth in the absence of a solvent, it is not necessary to individually solvent.This area
Those of ordinary skill easily determines this.Using in the case of solvent, any aprotic solvent can be used as available molten
Agent, if its can suitably solvent reaction material, reaction is not brought any adverse effect, and easily removes after reacting
Words.Such as, toluene, acetonitrile, oxolane (THF), methyl ethyl ketone (MEK), dimethylformamide (DMF), diformazan can be used
Sulfoxide (DMSO), dichloromethane (MC) etc., but it is not limited to this.These solvents can be used alone, or molten as two or more
The mixture of agent uses.Can not specifically limit the consumption of solvent, and be suitable to fully to dissolve reaction material and will not be to reaction
Have a negative impact required in the range of can use the solvent of appropriate amount and/or concentration.Consider above-mentioned main points, the common skill in this area
Art personnel can select the solvent of appropriate amount and/or concentration.
The reaction scheme of the novel epoxide according to illustrative embodiments is as follows.
Knowable to reaction equation above, synthesizing novel epoxy by the preparation method according to illustrative embodiments
During compound, by-product described within being concurrently formed at the bracket of reaction equation above.Mixture also can be deposited
At non-reacted parent material.
As reference, synthesize parent material also by the method well known to any the art.Such as, can pass through
Korean Patent Application No. 2012-93320,2013-11711,2013-27308,2013-that the present inventor submits to
Method described in 35546,2013-78347 and 2013-111473 synthesizes parent material, and the full content of above each literary composition passes through
Quote and include in herein.
(2) method 2
Such as, as mentioned above, it is necessary, prepared by following according to the epoxide of illustrative embodiments: parent material is (
There is the epoxide of epoxide group and hydroxyl or amido) the alkoxysilyl of thiazolinyl and non-reacted monosilane
Base.
Parent material, such as, have the epoxide of epoxide group and hydroxyl or amido, can be to have formula AS2 to arrive
The compound of OS2.
At least two in multiple substituent groups a2 of formula AS2 to FS2 is general formula E 2, and at least two in substituent group a2 is
Hydroxyl, and remaining substituent group a2 can be each independently selected from hydrogen (H) and formula A11.
At least two in multiple substituent groups a2 of formula GS2 to LS2 is general formula E 1, and at least two in substituent group a2 is
Hydroxyl, and remaining substituent group a2 can be hydrogen (H).
At least two in multiple substituent groups a2 of formula M S2 to OS2 is general formula E 2, and remaining substituent group a2 can be hydrogen
(H)。
In general formula D S2, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
In formula HS2, J is to be directly connected to group ,-CH2-orAnd Rx is hydrogen (H) or C1-C3 alkane
Base.
In formula IS2, K is selected from least one of lower group: formula 1a2 to 1f2.
In formula LS2, L isAnd,In, Ry is straight or branched C1-C10 alkyl.
In formula M S2, M is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, orR is hydrogen (H) or C1-C3 alkyl.
In formula IS2, when K is formula 2a to 2e, n is the integer of 3 or bigger, and when K is formula 2f, n is 2 or more
Big integer.
In formula JS2, n is the integer of two or more.
In formula KS2, n is the integer of 0 or bigger.
In formula LS2, when L isTime, n
It is the integer of 3 or bigger, when L isTime, n is the integer of two or more.
In formula LS2, p is 1 or 2.In formula IS2 to LS2, the maximum of n is 1,000.
Specifically, under conditions of there is optional solvent, carry out the hydroxyl of parent material or the alkoxyl first of amido
Silylation and non-reacted silylanizing, thus obtain and have at least two according to the illustrative embodiments in the present invention
Individual epoxide group, at least one alkoxysilyl and at least one non-reacted functional group (the most non-reacted first
Silylation and thiazolinyl) epoxide.
Because of carry out according to stoichiometry the hydroxyl of parent material or amido and have formula AS3 alkoxy silane it
Between reaction, it is contemplated that to stoichiometry, use 0.1 to 5 equivalent alcoxyls relative to hydroxyl or the amido of 1 equivalent parent material
Base silane, carries out the reaction between parent material and the alkoxy silane with formula AS3.
Specifically, as whole R of the alkoxy silane with formula AS31To R3When being methoxyl group, wherein relative to 1
The hydroxyl of equivalent parent material or amido use and are more than or equal to 0.1 equivalent and have the alkoxyl silicone of formula AS3 less than 1 equivalent
The reaction of alkane is preferred.In the case of being used below the alkoxy silane of concentration range, methoxysilyl anti-
The silylanizing degree answering speed and final epoxy composite structures can be too low.Using the alkoxyl silicone more than concentration range
In the case of alkane, the methoxysilyl concentration in final epoxy composite structures can be too high.
[formula AS3]
OCN-(CH2)m-SiR1R2R3
In formula AS3, R1To R3In at least one be C1 to C6 alkoxyl, preferably ethyoxyl, remaining R1Arrive
R3Being C1 to C10 alkyl, described alkoxyl and alkyl can be straight or branched, can be ring-type or acyclic, and can have or not
There is N, O, S, or P hetero atom.In addition, m is the integer of 1 to 10, the integer of preferably 3 to 6.
Additionally, because carrying out the hydroxyl of parent material or amido according to stoichiometry and there is the non-reaction of formula AS4
Property silane between reaction, it is contemplated that to stoichiometry, use 0.1 to 5 relative to hydroxyl or the amido of 1 equivalent parent material
The non-reacted silane of equivalent, carries out the reaction between parent material and non-reacted silane.
[formula AS4]
OCN-(CH2)m-SiR4R5R6
In formula AS4, R4To R6Be have the aliphatic of 1 to 20 carbon atoms, alicyclic or aryl moieties non-
Reactive group, non-reacted group can be straight or branched, can be ring-type or acyclic, and can with or without N, O, S,
Or P hetero atom.In addition, m is the integer of 1 to 10, the integer of preferably 3 to 6.
Reaction between parent material, alkoxy silane and non-reacted silane can comprise (1) parent material and alkoxyl
Silane and the reaction of non-reacted silane, comprise (2) parent material and the reaction of alkoxy silane simultaneously and reaction subsequently is produced
Thing and the reaction in-situ of non-reacted silane.
Parent material and the reaction temperature of alkoxy silane and response time can be depending on the kind of reaction material and change,
Such as reaction can carried out 1 hour to 72 hours at a temperature of-20 DEG C to 120 DEG C.By at the reaction temperatures, reaction is entered
In the row response time, required reaction can be completed.
According to circumstances needing, the reaction relating to the method preparing epoxide according to illustrative embodiments can be at alkali
Exist and carry out.Reaction can be carried out in the case of not using single alkali, and in this case, reaction rate declines,
Alkali can be used to increase reaction rate.Alkali used can include such as K2CO3,Na2CO3,KHCO3,NaHCO3, triethylamine, two is different
Propylethylamine etc., but it is not limited to this.These alkali can be used alone, or being applied in combination with two or more alkali.In view of anti-
Answer efficiency, the alkali of 1-5 equivalent can be used relative to the hydroxyl of 1 equivalent parent material or amido.
, according to circumstances need meanwhile, optionally use solvent.Such as, the viscosity of reaction material is fitted at the reaction temperatures
In the case of carrying out reacting without using single solvent, then can not use solvent.That is, when reaction material viscosity
Low to when making the mixing of reaction material and stir the carrying out that can smooth in the absence of a solvent, it is not necessary to individually solvent.
Those of ordinary skill in the art easily determine this.Using in the case of solvent, any aprotic solvent can be used as can
Solvent, if its can suitably solvent reaction material, reaction is not brought any adverse effect, and the easiest
If removing.Such as, toluene, acetonitrile, oxolane (THF), methyl ethyl ketone (MEK), dimethylformamide can be used
(DMF), dimethyl sulfoxide (DMSO), dichloromethane (MC) etc., but be not limited to this.These solvents can be used alone, or as two kinds
Or the mixture of more kinds of solvent uses.Can not specifically limit the consumption of solvent, and be suitable to fully to dissolve reaction material and
Proper amount of solvent can be used in the range of needed for reaction will not being had a negative impact.Considering above-mentioned main points, this area is common
Technical staff can select proper amount of solvent.
The reaction scheme of the novel epoxide according to the present invention is as follows.
A () is in the case of parent material comprises hydroxyl wherein:
B () is in the case of parent material comprises amido wherein:
Knowable to reaction scheme as above, at the epoxy compound using preparation in accordance with the present invention preparation novelty
During thing, also produce the as above by-product shown in text response scheme bracket.Also can there is unreacted parent material.
The method well known to the art that it be also possible to use is to synthesize parent material.Such as, can use and carried by the applicant
Korean Patent Application No. 2012-93320,2013-11711,2013-27308,2013-35546,2013-78347 handed over, and
Method described in 2013-111473 synthesizes parent material.The details of the description in patent application is as with reference to being included in this Shen
In please.
3. epoxy composite
According to another exemplary embodiment in the present invention, it is provided that epoxy composite, it comprises according in the present invention
On the one hand the novel epoxide provided.
Any compositions that the present invention provides can be used for various application, such as electronic material, if semiconductor substrate is (as integrated
Circuit (IC) base material or built up film), encapsulating material (encapsulating material), electronic component such as printed circuit board (PCB), adhesive, paint, multiple
Condensation material etc., but it is not limited to this.Additionally, the arbitrary composition that the present invention provides all can be as curable compositions and/or bag
The curable compositions including inorganic material provides.
As long as comprising the novel epoxide according to the illustrative embodiments in the present invention in epoxy composite,
Specifically it is selected from the epoxide of at least one novelty of formula AF to the OF according to the illustrative embodiments in the present invention,
The epoxy composite of the aspect according to as above or invention described below can comprise appointing well known to the art
The epoxide of meaning type and/or arbitrarily formula.In this case, firming agent, curing accelerator (catalysis can not be limited
Agent), inorganic material (filler) (such as, inorganic particle and/or fiber), other universal epoxy compound and epoxy composite comprise
The kind of other additive and mixed proportion.
Additionally, in the prior art, the application for controlling physical property and/or its purpose, epoxy combination are depended on
Thing, cured product and/or composite can be used together with various types of universal epoxy compounds.Therefore, according to as above institute
State or the epoxide of one side of invention described below can comprise selected from according to the exemplary embodiment party in the present invention
The epoxide (hereinafter referred to as ' epoxide in the present invention ') of at least one novelty of formula AF to the OF of formula, and
Epoxide (hereinafter referred to as ' the epoxy compound of the prior art well known to any type of the art can be comprised
Thing ') as epoxide.
The epoxide of prior art does not limit, but can any epoxide well known to the art.
Such as, epoxide of the prior art can be selected from least one of lower group: epoxide based on glycidyl ether,
Epoxide based on glycidyl, epoxide based on glycidyl amine, epoxidation based on ethylene oxidic ester
Compound, rubber modified epoxy compound, epoxide based on aliphatic polyglycidyl base and based on aliphatic shrink sweet
The epoxide of oleyl amine.In addition, epoxide of the prior art can be selected from least one of lower group: sweet based on shrinking
Oil the epoxide of ether, epoxide based on glycidyl, epoxide based on glycidyl amine, based on contracting
The epoxide of water glyceride, rubber modified epoxy compound, epoxide based on aliphatic polyglycidyl base and
Epoxide based on aliphatic glycidyl amine, its comprise bis-phenol, biphenyl, naphthalene, benzene, dihydroxy diphenyl sulfide, fluorenes, anthracene,
Isocyanuric acid ester, triphenyl methane, 1,1,2,2-tetraphenyl ethane, tetraphenylmethane, 4,4'-MDA, amino
Phenol, alicyclic compound, aliphatic compound or novolaks unit are as nuclear structure.
Such as, epoxide of the prior art can be selected from least one of lower group: ring based on glycidyl ether
Oxygen compound, epoxide based on glycidyl, epoxide based on glycidyl amine, based on ethylene oxidic ester
Epoxide, it comprises bis-phenol, biphenyl, naphthalene, benzene, dihydroxy diphenyl sulfide, fluorenes, anthracene, isocyanuric acid ester, triphenyl first
Alkane, 1,1,2,2-tetraphenyl ethane, tetraphenylmethane, 4,4'-MDA, amino-phenol, alicyclic compound, fat
Fat compounds of group or novolaks unit are as nuclear structure.
Such as, count on the basis of the gross weight of epoxide, any according to the illustrative embodiments in the present invention
Epoxy composite can comprise 1 weight % to 100 weight % epoxide in the present invention and 0 weight % to 99 weight % is existing
There is the epoxide in technology；Such as, 10 weight % to 100 weight % epoxide in the present invention and 0 weight %
To 90 weight % epoxides of the prior art；Such as, 30 weight % to 100 weight % epoxy compound in the present invention
Thing and 0 weight % are to 70 weight % epoxides of the prior art；Such as, 50 weight % to 100 weight % in the present invention
In epoxide and 0 weight % to 50 weight % epoxides of the prior art；Such as, 10 weight % are to being less than
100 weight % epoxide in the present invention and more than 0 weight % to 90 weight % epoxides of the prior art；
Such as, 30 weight % are to less than 100 weight % epoxide in the present invention and existing to 70 weight % more than 0 weight %
Epoxide in technology；Such as, 50 weight % are to less than 100 weight % epoxide in the present invention be more than
0 weight % is to 50 weight % epoxides of the prior art, but is not limited to this.
In addition, inorganic material can also be comprised according to any epoxy composite in terms of described above or invention described below
Such as, material (filler) (inorganic particle and/or fiber).
It is usable in association area any inorganic particle known to the physical property for strengthening organic resin.Inorganic
The example of granule may include but be not limited to selected from least one of lower group: at least one metal-oxide selected from lower group: dioxy
SiClx (including such as vitreous silica and crystalline silica), zirconium oxide, titanium oxide, aluminium oxide, silicon nitride and aluminium nitride and again
Half siloxanes (silsesquioxane).These inorganic particles can be used alone, or as two or more inorganic particles
Mixture uses.
In the case of a large amount of especially silicon dioxide of mixing, need to use vitreous silica.Vitreous silica can have fragmentation shape
Shape or spherical form.However, it is desirable to use spherical form to increase the mixed proportion of vitreous silica and the molten of suppression formation material
Body viscosity raises.
In view of the application of composite, the dispersibility etc. of inorganic particle specifically, can use granularity is 0.5 to receive
Rice is to the inorganic particle of tens microns (such as 50 microns-100 microns), but is not limited to this.Because inorganic particle dispersion is at epoxy
In compound and its dispersibility is different with granularity, so needing to use the inorganic particle with above-mentioned size in combination.This
Outward, need to increase the particle size distribution of inorganic particle to be mixed, increase the amount of inorganic particle in mixture.
In the epoxy composite according to the illustrative embodiments in the present invention, suitably can control relatively according to following
Amount in the inorganic particle that epoxide adds: the CTE of epoxy composite material declines, applying of epoxy composite and application thereof
Required appropriate viscosity.Such as, count on the basis of the gross weight of the solid content of epoxy composite and (produce at epoxy resin cure simultaneously
In the case of thing, count on the basis of the gross weight of epoxy resin-cured product), the amount of described inorganic particle can be 5-95 weight
Amount %, such as 5-90 weight %, such as 10-90 weight %, such as 30-95 weight %, such as 30-90 weight %, such as 5-60
Weight %, such as 10-50 weight %.
Specifically, in a kind of example embodiment, it is contemplated that CTE numerical value and materials processing ability, at epoxy combination
In the case of thing is used as enveloping semiconductor material etc., count on the basis of the gross weight of the solid content of epoxy composite (simultaneously at ring
In the case of epoxy resins cured product, count on the basis of the gross weight of epoxy resin-cured product), the amount of inorganic particle can as a example by
Such as 30 weight %-95 weight %, such as 30 weight %-90 weight %, but it is not limited to this.In a kind of example embodiment, examine
Consider to the CTE numerical value of base material and intensity etc., in the case of epoxy composite is used as semiconductor substrate etc., with epoxy composite
Count on the basis of the gross weight of solid content (simultaneously in the case of epoxy resin-cured product, total with epoxy resin-cured product
Count on the basis of weight), the amount of inorganic particle can be such as 5 weight %-85 weight %, such as 10 weight %-80 weight %, but not
It is limited to this.
Meanwhile, in the case of wherein fiber being used as inorganic material, because generally to impregnate fiber with epoxy composite
Mode prepare composite, so being not particularly limited the size etc. of fiber.Additionally, can use commonly used in the art any
Type and the fiber of size.
It is usable in association area any commonly employed fiber for improving organic resin cured article physical property, but not
It is limited to this.Specifically, glass fibre, organic fiber or their mixture can be used.Additionally, term use herein
" glass fibre " can include the glass fiber cloth of weaving, the glass fiber cloth etc. of nonwoven and glass fibre.Glass fibre
Example can include, but are not limited to: E glass fibre, T glass fibre, S glass fibre, NE glass fibre, D glass fibre, quartz
Glass fibre etc..Such as, E glass fibre or T glass fibre can wherein be included.Organic fiber can be but be not limited to selected from lower group
A kind of: liquid crystalline polyester fiber, dacron fibre, full aromatics fiber, polybenzoxazole fibers, nylon fiber,
PEN fiber, polypropylene fibre, polyether sulfone fiber, polyvinylidene fluoride fiber, polyethylene sulfide fiber
And polyetheretherketonefiber fiber.These fibers can be used alone, or uses with two or more forms combined.
Count on the basis of the gross weight of described cured article, (such as exist in the epoxy composite according to aspect of the present invention
In glass fiber compound material), the amount of fiber can be 10-90 weight %, such as 30-70 weight %, the most such as 35-70 weight
Amount %.Therefore, resin content can be 10-90 weight %, such as 30-70 weight %, the most such as 35-70 weight %.Consider
To increase and the working ability aspect of thermostability, fibre weight needs within the scope of above-mentioned.Meanwhile, at fibrous epoxy combination
In thing, cured product etc., the solid content part getting rid of fiber from total solid content is referred to as resin content (R/C).
Additionally, according in the fibrous epoxy composite of aspect of the present invention, according to circumstances need to comprise extraly
Inorganic particle.In such case, it is contemplated that physical property and the improvement of working ability, on the basis of the weight of resin content
Meter, inorganic particle can mix with epoxy composite with the amount of 1 weight %-80 weight %.In this case, it is not particularly limited
Spendable inorganic particle type, and any inorganic particle well known to the art can be used.Such as, above-mentioned class can be used
The inorganic particle of type.
Meanwhile, in the epoxy composite of the aspect of described above or invention described below, can comprise solid extraly
Agent.
Any firming agent being commonly known for the firming agent of epoxide can be used as described firming agent, but be not limited to
This, such as, can use amine, polyphenol (polyphenol), anhydride etc..
Specifically, the polyamines (polyamine) of aliphatic amine, cycloaliphatic amines, aromatic amine, other amine and modification can use
Make amine hardener, but be not limited to this.Additionally, the amines including two or more primary amine groups can be used.Amine hardener
Concrete example can include at least one aromatic amine selected from lower group: 4,4'-dimethylaniline (diaminodiphenyl-methane, DAM
Or DDM), DADPS (DDS) and m-diaminobenzene.；At least one aliphatic amine selected from lower group: diethylenetriamines
(DETA), diethylene tetramine, trien (TETA), m-xylenedimaine (MXDA), methane diamidogen (MDA), N,
N'-diethylenediamine (N, N'-DEDA), tetren (TEPA) and hexamethylene diamine；Selected from lower group at least one
Kind cycloaliphatic amines: isophorone diamine (IPDI), N-aminoethyl piperazine (AEP), double (4-amino-3-methylcyclohexyl) methane；Other amine such as dicyandiamide (DICY) etc.；And the amine of modification such as compound based on polyamide, base
Compound etc. in epoxide.
The example of polyphenol firming agent may include but be not limited to phenol novolacs, cresol novolac resin, bisphenol-A phenolic
Resin, xylenols urea formaldehyde, triphenyl phenolic resin, xenol urea formaldehyde, dicyclopentadiene phenolic resin, napthalinic phenolic resins
Deng.
The example of firming agent based on anhydride may include but be not limited to aliphatic anhydride, such as dodecenylsuccinic acid acid anhydride
(DDSA), poly-nonyl dimerization anhydride (poly azelaic poly anhydride) etc.；Alicyclic anhydride such as hexahydro O-phthalic
Anhydride (HHPA), methyl tetrahydrophthalic anhydride (MeTHPA), methylnadic anhydride (methylnadic anhydride)
(MNA) etc.；Aromatic anhydride such as trimellitic anhydride (TMA), pyromellitic acid anhydride (PMDA), benzophenone tetracarboxylic dianhydride
(benzophenonetetracarboxylic dianhydride) (BTDA) etc.；And anhydride such as tetrabromo phthalein of based on halogen
Anhydride (TBPA), chlorendic anhydride etc..
In general, the solidification of epoxy resin composite material can be controlled by the extent of reaction of firming agent and epoxide group
Degree.According to the scope of target state of cure, the concentration of epoxide group based on epoxide the amount of firming agent can be controlled.
Such as, when using amine hardener in the firming agent equivalent reaction with epoxy radicals, the ratio of epoxide equivalent/amine equivalent needs control
System is to 0.5-2.0, or such as 0.8-1.5.
Use amine hardener as example, it is provided that about the description of the combined amount of firming agent.But, by according to required
The state of cure of scope, concentration based on epoxide group total in epoxy composite, the ring of the amount of mixing suitable stoichiometric ratio
Oxygen functional group and the reactive functional groups of firming agent, can use in polyphenol firming agent, firming agent based on anhydride and the present invention and not have
There is independent description but for any firming agent of cured epoxy compound.Key element described above is known in the field.
Additionally, imidazoles as described below is typically used as curing accelerator, but also can alone serve as firming agent.Wherein will
In the case of imidazoles is used as firming agent, 0.1phr to 10phr imidazoles can be used relative to epoxide.
According to circumstances need, in the epoxy composite of the aspect according to described above or invention described below, can
Include optional curing accelerator (curing catalysts) extraly, to promote curing reaction.Additionally, can be solid by this area is used for
Any commonly employed catalyst changing epoxy composite is used as curing accelerator (curing catalysts).Can use but be not limited to such as miaow
Azoles, tertiary amine, quaternary ammonium, acylate, lewis acid, phosphorus-containing compound etc. are as curing accelerator.
Specifically, imidazoles, such as N, N-dimethyl benzylamine, 2-methylimidazole (2MZ), 2-undecyl can such as be used
Imidazoles, 2-ethyl-4-methylimidazole (2E4M), 2-phenylimidazole, 1-(2-cyanoethyl) 2-alkyl imidazole, 2 heptadecyl imidazole
(2HDI) etc.；Tertiary amine compound, such as benzyl dimethyl amine (BDMA), three (dimethylaminomethyl) phenol (DMP-30), diaza
Ring hendecene (diazacycloundecene) (DBU), triethylenediamine etc.；Quaternary ammonium salt, such as Tetrabutylammonium bromide etc.；Phenodiazine
The acylate of heterocycle hendecene (DBU)；Phosphorio compound, such as triphenylphosphine, phosphate ester etc.；And lewis acid such as BF3-mono-
Ethamine (BF3-MEA) etc., but it is not limited to this.Because its microencapsulation coating, complex salt formation etc., these can be used potentially to solidify
Accelerator.According to condition of cure, these compounds can be used alone, or the form of mixtures as two or more uses.
Combined amount that can be commonly used in the art, uses the amount of mixing cured accelerator, but is not limited to this.Such as, with ring
Counting on the basis of oxygen compound, the amount of mixing cured accelerator can be that (number/100 part resin, with 100 weight for 0.1phr-10phr
The weight portion of meter on the basis of part epoxide), such as 0.2phr-5phr.Consider curing reaction facilitation effect and curing reaction
Rate controlled aspect, needs to use the amount of curing accelerator as above.By using mixing cured promotion as above
The scope of the amount of agent, can be rapidly carried out solidification, and can expect raising flux.
In epoxy composite, according to circumstances need, within the scope of the physical property not damaging epoxy composite, can
Mix such as releasing agent, surface conditioning agent, fire retardant, plasticizer, antibacterial, levelling agent (leveling agent), defoamer,
Other additive of coloring agent, stabilizer, coupling agent, viscosity-control additive, diluent, rubber, thermoplastic resin etc., with common control
The physical property of epoxy composite processed.
Such as, in order to improve the flexibility of the compositions according to illustrative embodiments, can be by rubber and/or thermoplastic resin
Add to according on the one hand to epoxy composite.The ring of thermoplastic resin well known to the art and modified rubber can be used
Epoxy resins.As long as rubber is not dissolved by solvent used in compositions and keeps dispersity in the composition, this skill can be used
Any rubber well known to art field is as rubber.This kind of rubber can include, such as acrylonitrile butadiene rubber, butadiene rubber
Glue, acryl rubber (acryl rubber), the rubber grain of core-shell structure copolymer type, the acrylonitrile butadiene rubber granule of crosslinking,
The styrene butadiene ribber granule of crosslinking, acryl rubber granule etc., but it is not limited to this.These materials can be used alone,
Or being applied in combination with two or more materials.In the case of using rubber grain, it is contemplated that improve physical property, averagely
Granularity needs for 0.005-1 micron, more specifically 0.2-0.6 micron.In view of physical property, such as consolidating with epoxy composite
Count on the basis of the weight of content, mixed rubber granule can be carried out with the amount of 0.5 weight %-10 weight %.
As thermoplastic resin, can use but be not limited to phenoxy resin, polyvinyl acetal resin, polyimides tree
Fat, polyamide-imide resin, polyethersulfone resin, polysulfone resin etc..These materials can be used alone, or as two or more
The mixture planting material uses.In view of physical property, such as, count on the basis of the weight of the solid content of epoxy composite, permissible
0.5 weight %-60 weight %, the amount of more specifically 3 weight %-50 weight % carry out mixed thermoplastic resin.
As mentioned above, it is necessary, the term " epoxy composite " used in the present invention should be understood to comprise the example according in the present invention
Property embodiment epoxide and according to circumstances need form epoxy composite other composition, the most according to circumstances need
This area to be mixed such as, except optional firming agent, curing accelerator (catalyst), inorganic material (filler) (inorganic particulate
Grain and/or fiber), other additive beyond other universal epoxy compound and solvent.Therefore, epoxy composite is generally considered
Working ability etc., optionally use in epoxy composite solvent suitably control epoxy composite solid content and/
Or its viscosity.Meanwhile, in the present invention, term " gross weight of the solid content of epoxy composite " refers at composition epoxy composite
In component, the gross weight of the component in addition to solvent.
Can be by any epoxy composite provided the according to aspects of the present invention compositions acting on electronic material.Described
Electronic material may include but be not limited to such as be arranged on use for the base material of quasiconductor, film, pre impregnated material, wherein metal level
Suprabasil laminate, encapsulating material that compositions according to a kind of example embodiment in the present invention is formed (encapsulate material
Material), electronic building brick such as printed circuit board (PCB) etc..Additionally, described epoxy composite can be used for various application, such as adhesive, paint, again
Condensation material etc..Another kind of illustrative embodiments according to the present invention, it is provided that electronic material, described electronic material comprises containing basis
The epoxy composite of the epoxide of a kind of example embodiment in the present invention, or use described epoxy composite to carry out shape
Become.Further it is provided that semiconductor device, described semiconductor device includes described electronic material, or needs to use described electronics material
Material is formed, or uses described electronic material to be formed.Specifically, described semiconductor device can be to include printed circuit board (PCB)
Semiconductor device (such as, at the printed circuit board (PCB) of semiconductor element installed above) and/or include semiconductor sealing material
Semiconductor device, it epoxy composite including containing the epoxide according to a kind of example embodiment in the present invention, or
Person needs to use described compositions to be formed, or uses described compositions to be formed.In addition, it is possible to provide cured product, gluing
Agent, paint or composite, described cured article, adhesive, paint or composite are included in the aspect of the present invention offer
Any epoxy composite, or need to use described compositions to be formed, or use described compositions to be formed.
According to the another kind of illustrative embodiments in the present invention, it is possible to provide cured article, described cured article is included in
The epoxy composite according to a kind of example embodiment in the present invention provided in an aspect of of the present present invention, or need to use
Described compositions is formed, or uses described compositions to be formed.At the actually used ring provided in the aspect of the present invention
In the case of oxygen compositions, such as in the case of described epoxy composite is actually used as electronic material etc., produce as solidification
Thing uses described epoxy composite.In the art, generally comprising epoxide and filler (it is inorganic component)
The cured product that compositions is formed is referred to as composite.
The epoxide provided in exemplary embodiment of the invention as above can have in the composite
Excellent heat resistance character and/or can have excellent flame retardancy in cured product.
Specifically, described composite can show relatively low CTE, e.g., less than or equal to 15ppm/ DEG C, e.g., less than or
Equal to 12ppm/ DEG C, e.g., less than or equal to 10ppm/ DEG C, e.g., less than or equal to 8ppm/ DEG C, e.g., less than or equal to 6ppm/
DEG C, e.g., less than or equal to 4ppm/ DEG C.Because CTE numerical value reduces, the physical property of composite is improved, and does not thus have
It is particularly limited to the lower limit of CTE numerical value.
Such as, any epoxide according to a kind of example embodiment in the present invention is comprised, as inorganic material
Glass fibre (such as E glass fibre and/or T glass fibre) and resin content be 30 weight %-60 weight % (resin contents
Can include or not include inorganic particle) composite can present e.g., less than or equal to 10ppm/ DEG C, e.g., less than or equal to
The CTE of 8ppm/ DEG C, e.g., less than or equal to 6ppm/ DEG C, e.g., less than or equal to 4ppm/ DEG C.
Additionally, such as, any epoxide according to a kind of example embodiment in the present invention is comprised as epoxy
Compound, (such as, 60 weight % are to 80 weight %, and such as, 70 weight % are to the silicon dioxide of 80 weight % to comprise inorganic particle
Grain) as the composite of inorganic material can present e.g., less than or equal to 20ppm/ DEG C, e.g., less than or equal to 15ppm/ DEG C,
E.g., less than or equal to 10ppm/ DEG C, e.g., less than or equal to 8ppm/ DEG C, e.g., less than or equal to 6ppm/ DEG C, the least
In or equal to the CTE of 4ppm/ DEG C.
Additionally, according to the composite (cured product containing inorganic material) of a kind of example embodiment in the present invention
Tg can be higher than 100 DEG C, such as greater than or equal to 130 DEG C, the most such as greater than or equal to 250 DEG C.Otherwise, composite can be nothing
Tg's.Because Tg numerical value is higher, the physical property of composite is improved, and is thus not particularly limited the upper limit of CTE numerical value.
Meanwhile, (the solidification product of inorganic material is not comprised according to the cured product of the epoxide of illustrative embodiments
Thing) can have the CTE of 50ppm/ DEG C to 150ppm/ DEG C.
In this application, with scope limit numerical value include any subrange in lower numerical limit, limit value, scope,
And whole numerals that this scope includes, unless expressly stated otherwise,.Such as, C1-C10 should be understood to include C1, C2, C3,
C4, C5, C6, C7, C8, C9 and C10's is whole.Additionally, in the feelings of the lower numerical limit or limit value not defining numerical range
Under condition, it should be understood that the value becoming smaller or greater can provide better properties.Further, it should be understood that when not defining the limit, can wrap
Include arbitrary value.Such as, the CTE less than or equal to 4ppm/ DEG C should be understood to be included in all values of this scope, such as 4, and 3.5,3,
2.7,2,1.4,1,0.5ppm/ the CTE of DEG C grade.
Hereafter will describe the present invention in detail by embodiment.Following example are used for illustrating the present invention, but are not intended to this
Invention is construed as limiting.
Synthetic example 1: synthesize the epoxy compound comprising triethoxysilyl and ethyl silicane base based on bisphenol-A
Thing (Si (OEt)3:Si(Et)3=3:1)
Add to 500 milliliters of flasks and the bisphenol A epoxide (structural formula 1) with pi-allyl of mixing 17.17g,
The triethoxysilane of 11.01 milliliters, the triethyl silicane of 6.54 milliliters, the platinum oxide of 185 milligrams and the toluene of 150 milliliters,
Stir 24 hours at 85 DEG C the most under argon gas.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove
Go solvent to obtain final epoxide.The NMR data of gained end product is as follows.
[structural formula 1]
1H NMR(400MHz,CDCl3): δ=0.42-0.53 (m, 10H), 0.84 (t, J=8.0Hz, 4.5H), 1.20 (t,
J=7.0Hz, 13.5H), 1.60 (s, 6H), 1.62-1.72 (m, 4H), 2.61 (t, J=7.6Hz, 4H), 2.74 (dd, J=
2.6Hz, 2H), 2.86 (dd, J=4.2Hz, 2H), 3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 6H),
3.97 (dd, J=5.2Hz, 2H), 4.14 (dd, J=3.2Hz, 2H), 6.70 (d, J=7.6Hz, 2H), 6.94 (dd, J=
2.8Hz, 2H), 6.99 (d, J=7.6Hz, 2H).
Synthetic example 2: synthesize triethoxysilyl, ethyl silicane base and the pi-allyl of comprising based on bisphenol-A
Epoxide (Si (OEt)3:Si(Et)3: pi-allyl=2:1:1)
Add to 500 milliliters of flasks and the bisphenol A epoxide (structural formula 1) with pi-allyl of mixing 17.17g,
The triethoxysilane of 7.34 milliliters, the triethyl silicane of 3.27 milliliters, the platinum oxide of 185 milligrams and the toluene of 150 milliliters, so
After under argon gas at 85 DEG C stir 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove
Solvent obtains final epoxide.The NMR data of gained end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.42-0.53 (m, 9H), 0.84 (t, J=8.0Hz, 4.5H), 1.20 (t, J
=7.0Hz, 9H), 1.60 (s, 6H), 1.62-1.72 (m, 3H), 2.61 (t, J=7.6Hz, 3H), 2.74 (dd, J=2.6Hz,
2H), 2.86 (dd, J=4.2Hz, 2H), 3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 4H), 3.97
(dd, J=5.2Hz, 2H), 4.14 (dd, J=3.2Hz, 2H), 4.93-5.01 (m, 1H), 5.80-5.95 (m, 0.5H), 6.59-
6.71(m,0.4H),6.87-7.04(m,5.6H)。
Synthetic example 3: synthesize the epoxide (Si comprising triethoxysilyl and pi-allyl based on bisphenol-A
(OEt)3: pi-allyl=1:1)
Add to 500 milliliters of flasks and the mixing bisphenol A epoxide (structural formula 1) with pi-allyl of 5.31g, 2.33
Triethoxysilane, the platinum oxide of 28 milligrams and the toluene of 100 milliliters of milliliter, stirs 24 little the most under argon gas at 85 DEG C
Time.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxide.Institute
The NMR data obtaining end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 2H), 1.20 (t, J=7.0Hz, 9H), 1.60 (s,
6H), 1.62-1.72 (m, 2H), 2.61 (t, J=7.6Hz, 2H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=
4.2Hz, 2H), 3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 6H), 3.97 (dd, J=5.2Hz, 2H),
4.14 (dd, J=3.2Hz, 2H), 4.93-5.01 (m, 2H), 5.80-5.95 (m, 1H), 6.87-7.04 (m, 6H).
Synthetic example 4: synthesize the epoxide (Si comprising triethoxysilyl and pi-allyl based on bisphenol-A
(OEt)3: pi-allyl=1:1.5)
Add to 500 milliliters of flasks and the bisphenol A epoxide (structural formula 1) with pi-allyl of mixing 10.66g,
The triethoxysilane of 3.59 milliliters, the platinum oxide of 58 milligrams and the toluene of 100 milliliters, stir the most under argon gas at 85 DEG C
24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxidation
Thing.The NMR data of gained end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 1.6H), 1.20 (t, J=7.0Hz, 7.2H), 1.60
(s, 6H), 1.62-1.72 (m, 1.6H), 2.61 (t, J=7.6Hz, 1.6H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J
=4.2Hz, 2H), 3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 4.8H), 3.97 (dd, J=5.2Hz,
2H), 4.14 (dd, J=3.2Hz, 2H), 4.93-5.01 (m, 2.4H), 5.80-5.95 (m, 1.2H), 6.87-7.04 (m, 6H).
Synthetic example 5: synthesize the epoxide (Si comprising triethoxysilyl and pi-allyl based on bisphenol-A
(OEt)3: pi-allyl=1:0.67)
Add to 500 milliliters of flasks and the mixing bisphenol A epoxide (structural formula 1) with pi-allyl of 7.11g, 3.90
Triethoxysilane, the platinum oxide of 45 milligrams and the toluene of 100 milliliters of milliliter, stirs 24 little the most under argon gas at 85 DEG C
Time.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxide.Institute
The NMR data obtaining end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 2.4H), 1.20 (t, J=7.0Hz, 10.8H), 1.60
(s, 6H), 1.62-1.72 (m, 2.4H), 2.61 (t, J=7.6Hz, 2.4H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J
=4.2Hz, 2H), 3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 7.2H), 3.97 (dd, J=5.2Hz,
2H), 4.14 (dd, J=3.2Hz, 2H), 4.93-5.01 (m, 1.6H), 5.80-5.95 (m, 0.8H), 6.87-7.04 (m, 6H).
Synthetic example 6: synthesize the epoxide (Si comprising triethoxysilyl and pi-allyl based on bisphenol-A
(OEt)3: pi-allyl=1:0.33)
Add to 500 milliliters of flasks and the bisphenol A epoxide (structural formula 1) with pi-allyl of mixing 12.68g,
The triethoxysilane of 8.34 milliliters, the platinum oxide of 102 milligrams and the toluene of 100 milliliters, stir the most under argon gas at 85 DEG C
Mix 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxidation
Thing.The NMR data of gained end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 3H), 1.20 (t, J=7.0Hz, 13.5H), 1.60 (s,
6H), 1.62-1.72 (m, 3H), 2.61 (t, J=7.6Hz, 3H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=
4.2Hz, 2H), 3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 9H), 3.97 (dd, J=5.2Hz, 2H),
4.14 (dd, J=3.2Hz, 2H), 4.93-5.01 (m, 1H), 5.80-5.95 (m, 0.5H), 6.87-7.04 (m, 6H).
Synthetic example 7: synthesize the epoxide (Si comprising methoxysilyl and pi-allyl based on bisphenol-A
(OMe)3: pi-allyl=1:9)
Add to 500 milliliters of flasks and the bisphenol A epoxide (structural formula 1) with pi-allyl of mixing 40.09g,
The trimethoxy silane of 2.74 milliliters, the platinum oxide of 218 milligrams and the toluene of 100 milliliters, stir the most under argon gas at 85 DEG C
Mix 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxidation
Thing.The NMR data of gained end product is as follows.
1H NMR (400MHz, DMSO): δ=0.54 (t, J=8.0Hz, 0.4H), 1.55 (s, 6.4H), 2.49-2.51
(m, 0.4H), 2.70 (dd, J=2.6Hz, 2H), 2.82 (dd, J=4.2Hz, 2H), 3.26-3.32 (m, 5.4H), 3.42 (s,
1.8H), 3.84 (dd, J=5.4Hz, 2H), 4.26 (dd, J=3.2Hz, 2H), 4.94-5.01 (m, 3.6H), 5.83-5.95
(m,1.8H),6.83-7.02(m,6H)。
Synthetic example 8: synthesize the epoxide (Si comprising methoxysilyl and pi-allyl based on bisphenol-A
(OMe)3: pi-allyl=1:4)
Add to 500 milliliters of flasks and the bisphenol A epoxide (structural formula 1) with pi-allyl of mixing 11.10g,
The trimethoxy silane of 11.86 milliliters, the platinum oxide of 59 milligrams and the toluene of 100 milliliters, stir the most under argon gas at 85 DEG C
Mix 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxidation
Thing.The NMR data of gained end product is as follows.
1H NMR (400MHz, DMSO): δ=0.54 (t, J=8.0Hz, 0.8H), 1.55 (s, 6.8H), 2.49-2.51
(m, 0.8H), 2.70 (dd, J=2.6Hz, 2H), 2.82 (dd, J=4.2Hz, 2H), 3.26-3.32 (m, 4.8H), 3.42 (s,
3.6H), 3.84 (dd, J=5.4Hz, 2H), 4.26 (dd, J=3.2Hz, 2H), 4.94-5.01 (m, 3.2H), 5.83-5.95
(m,1.6H),6.83-7.02(m,6H)。
Synthetic example 9: synthesize and based on bisphenol-A comprise triethoxysilyl, methoxysilyl and pi-allyl
Epoxide (Si (OEt)3:Si(OMe)3: pi-allyl=1:1:8)
Add to 500 milliliters of flasks and the bisphenol A epoxide (structural formula 1) with pi-allyl of mixing 40.02g,
The triethoxysilane of 3.68 milliliters, the trimethoxy silane of 2.73 milliliters, the platinum oxide of 218 milligrams and the toluene of 100 milliliters,
Stir 24 hours at 85 DEG C the most under argon gas.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove
Go solvent to obtain final epoxide.The NMR data of gained end product is as follows.
1H NMR (400MHz, DMSO): δ=0.50-0.56 (m, 0.8H), 1.04-1.13 (m, 1.8H), 1.55 (s,
6.8H), 2.49-2.51 (m, 0.8H), 2.70 (dd, J=2.6Hz, 2H), 2.82 (dd, J=4.2Hz, 2H), 3.26-3.32
(m, 4.8H), 3.42 (t, J=4.0Hz, 1.8H), 3.84 (dd, J=5.4Hz, 2H), 4.26 (dd, J=3.2Hz, 2H),
4.94-5.01(m,3.2H),5.83-5.95(m,1.6H),6.83-7.02(m,6H)。
Synthetic example 10: synthesize the epoxide comprising triethoxysilyl and ethyl silicane base based on naphthalene
(Si(OEt)3:Si(Et)3=3:1)
Add to 500 milliliters of flasks and the mixing naphthalene epoxy (structural formula 2) with pi-allyl of 18.66g, 13.32
Triethoxysilane, the triethyl silicane of 8.45 milliliters, the platinum oxide of 239 milligrams and the toluene of 150 milliliters of milliliter, then exists
Stir 24 hours at 85 DEG C under argon.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent
Obtain final epoxide.The NMR data of gained end product is as follows.
[structural formula 2]
1H NMR(400MHz,CDCl3): δ=0.64-0.72 (m, 10H), 0.84 (t, J=8.0Hz, 4.5H), 1.20 (t,
J=7.0Hz, 13.5H), 1.62-1.72 (m, 4H), 2.61 (t, J=7.6Hz, 4H), 2.74 (dd, J=2.6Hz, 2H), 2.86
(dd, J=4.2Hz, 2H), 3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 6H), 3.97 (dd, J=
5.2Hz, 2H), 4.14 (dd, J=3.2Hz, 2H), 7.28 (d, J=8.5Hz, 2H), 7.75 (d, J=8.5Hz, 2H).
Synthetic example 11: synthesize and based on naphthalene comprise triethoxysilyl, ethyl silicane base and the ring of pi-allyl
Oxygen compound (Si (OEt)3:Si(Et)3: pi-allyl=2:1:1)
Add to 500 milliliters of flasks and the mixing naphthalene epoxy (structural formula 2) with pi-allyl of 18.66g, 9.51 millis
Triethoxysilane, the triethyl silicane of 4.23 milliliters, the platinum oxide of 239 milligrams and the toluene of 150 milliliters risen, then at argon
Stir 24 hours at 85 DEG C under gas.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent
Obtain final epoxide.The NMR data of gained end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.64-0.72 (m, 7.5H), 0.84 (t, J=8.0Hz, 2.3H), 1.20
(t, J=7.0Hz, 9H), 1.62-1.72 (m, 3H), 2.61 (t, J=7.6Hz, 3H), 2.74 (dd, J=2.6Hz, 2H), 2.86
(dd, J=4.2Hz, 2H), 3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 4.5H), 3.97 (dd, J=
5.2Hz, 2H), 4.14 (dd, J=3.2Hz, 2H), 5.07-5.12 (m, 1H), 5.98-6.08 (m, 0.5H), 7.28 (d, J=
8.5Hz, 2H), 7.75 (d, J=8.5Hz, 2H).
Synthetic example 12: synthesize the epoxide (Si comprising triethoxysilyl and pi-allyl based on naphthalene
(OEt)3: pi-allyl=1:1)
Add to 500 milliliters of flasks and the mixing naphthalene epoxy (structural formula 2) with pi-allyl of 18.39g, 9.63 millis
Triethoxysilane, the platinum oxide of 119 milligrams and the toluene of 100 milliliters risen, stirs 24 little the most under argon gas at 85 DEG C
Time.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxide.Institute
The NMR data obtaining end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 2H), 1.20 (t, J=7.0Hz, 9H), 1.62-1.72
(m, 2H), 2.61 (t, J=7.6Hz, 2H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=4.2Hz, 2H), 3.30-
3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 6H), 3.97 (dd, J=5.2Hz, 2H), 4.14 (dd, J=
3.2Hz,2H),5.07-5.12(m,2H),5.98-6.08(m,1H),7.28-7.35(m,2H),7.75-7.89(m,2H)。
Synthetic example 13: synthesize the epoxide (Si comprising triethoxysilyl and pi-allyl based on naphthalene
(OEt)3: pi-allyl=1:3)
Add to 500 milliliters of flasks and the mixing naphthalene epoxy (structural formula 2) with pi-allyl of 10.21g, 2.67 millis
Triethoxysilane, the platinum oxide of 66 milligrams and the toluene of 100 milliliters risen, stirs 24 little the most under argon gas at 85 DEG C
Time.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxide.Institute
The NMR data obtaining end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 1H), 1.20 (t, J=7.0Hz, 4.5H), 1.62-
1.72 (m, 1H), 2.61 (t, J=7.6Hz, 1H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=4.2Hz, 2H),
3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 3H), 3.97 (dd, J=5.2Hz, 2H), 4.14 (dd, J
=3.2Hz, 2H), 5.07-5.12 (m, 3H), 5.98-6.08 (m, 1.5H), 7.28-7.35 (m, 2H), 7.75-7.89 (m,
2H)。
Synthetic example 14: synthesize the epoxide (Si comprising triethoxysilyl and pi-allyl based on naphthalene
(OEt)3: pi-allyl=1:0.33)
Add to 500 milliliters of flasks and the mixing naphthalene epoxy (structural formula 2) with pi-allyl of 12.51g, 9.82 millis
Triethoxysilane, the platinum oxide of 121 milligrams and the toluene of 100 milliliters risen, stirs 24 little the most under argon gas at 85 DEG C
Time.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxide.Institute
The NMR data obtaining end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 3H), 1.20 (t, J=7.0Hz, 13.5H), 1.62-
1.72 (m, 3H), 2.61 (t, J=7.6Hz, 3H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=4.2Hz, 2H),
3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 9H), 3.97 (dd, J=5.2Hz, 2H), 4.14 (dd, J
=3.2Hz, 2H), 5.07-5.12 (m, 1H), 5.98-6.08 (m, 0.5H), 7.28-7.35 (m, 2H), 7.75-7.89 (m,
2H)。
Synthetic example 15: synthesize the epoxide (Si comprising methoxysilyl and pi-allyl based on naphthalene
(OMe)3: pi-allyl=1:9)
Add to 500 milliliters of flasks and the mixing naphthalene epoxy (structural formula 2) with pi-allyl of 13.52g, 0.98 milli
Trimethoxy silane, the platinum oxide of 88 milligrams and the toluene of 100 milliliters risen, stirs 24 little the most under argon gas at 85 DEG C
Time.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxide.Institute
The NMR data obtaining end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.72-0.77 (m, 0.4H), 1.73-1.80 (m, 0.4H), 2.61 (t, J=
7.6Hz, 0.4H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=4.2Hz, 2H), 3.30-3.34 (m, 2H), 3.58 (s,
1.8H), 3.97 (dd, J=5.2Hz, 2H), 4.14 (dd, J=3.2Hz, 2H), 5.07-5.12 (m, 3.6H), 5.98-6.08
(m,1.8H),7.28-7.35(m,2H),7.75-7.89(m,2H)。
Synthetic example 16: synthesize the epoxy compound comprising triethoxysilyl and ethyl silicane base based on biphenyl
Thing (Si (OEt)3:Si(Et)3=3:1)
Add to 500 milliliters of flasks and the mixing cyclohexyl biphenyl oxide (structural formula 3) with pi-allyl of 14.76g, 9.32
Triethoxysilane, the triethyl silicane of 5.54 milliliters, the platinum oxide of 156 milligrams and the toluene of 150 milliliters of milliliter, then exists
Stir 24 hours at 85 DEG C under argon.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent
Obtain final epoxide.The NMR data of gained end product is as follows.
[structural formula 3]
1H NMR(400MHz,CDCl3): δ=0.42-0.53 (m, 10H), 0.84 (t, J=8.0Hz, 4.5H), 1.20 (t,
J=7.0Hz, 13.5H), 1.62-1.72 (m, 4H), 2.61 (t, J=7.6Hz, 4H), 2.74 (dd, J=2.6Hz, 2H), 2.86
(dd, J=4.2Hz, 2H), 3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 6H), 3.97 (dd, J=
5.2Hz, 2H), 4.14 (dd, J=3.2Hz, 2H), 6.70 (d, J=7.6Hz, 2H), 6.94 (dd, J=2.8Hz, 2H), 6.99
(d, J=7.6Hz, 2H).
Synthetic example 17: synthesize triethoxysilyl, ethyl silicane base and the pi-allyl of comprising based on biphenyl
Epoxide (Si (OEt)3:Si(Et)3: pi-allyl=2:1:1)
Add to 500 milliliters of flasks and the mixing cyclohexyl biphenyl oxide (structural formula 3) with pi-allyl of 14.76g, 6.21
Triethoxysilane, the triethyl silicane of 2.77 milliliters, the platinum oxide of 156 milligrams and the toluene of 150 milliliters of milliliter, then exists
Stir 24 hours at 85 DEG C under argon.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent
Obtain end product, i.e. comprise the cyclohexyl biphenyl oxide of alkoxysilyl and aIkylsilyl groups.Gained end product
NMR data as follows.
1H NMR(400MHz,CDCl3): δ=0.42-0.53 (m, 9H), 0.84 (t, J=8.0Hz, 4.5H), 1.20 (t, J
=7.0Hz, 9H), 1.62-1.72 (m, 3H), 2.61 (t, J=7.6Hz, 3H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd,
J=4.2Hz, 2H), 3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 4H), 3.97 (dd, J=5.2Hz,
2H), 4.14 (dd, J=3.2Hz, 2H), 4.93-5.01 (m, 1H), 5.80-5.95 (m, 0.5H), 6.59-6.71 (m, 0.4H),
6.87-7.04(m,5.6H)。
Synthetic example 18: synthesize the epoxide (Si comprising triethoxysilyl and pi-allyl based on biphenyl
(OEt)3: pi-allyl=1:1)
Add to 500 milliliters of flasks and the cyclohexyl biphenyl oxide (structural formula 3) with pi-allyl of mixing 32.84g,
The triethoxysilane of 16.00 milliliters, the platinum oxide of 197 milligrams and the toluene of 100 milliliters, stir the most under argon gas at 85 DEG C
Mix 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxidation
Thing.The NMR data of gained end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 2H), 1.20 (t, J=7.0Hz, 9H), 1.62-1.72
(m, 2H), 2.61 (t, J=7.6Hz, 2H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=4.2Hz, 2H), 3.30-
3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 6H), 3.97 (dd, J=5.2Hz, 2H), 4.14 (dd, J=
3.2Hz,2H),4.93-5.01(m,2H),5.80-5.95(m,1H),6.87-7.04(m,6H)。
Synthetic example 19: synthesize the epoxide (Si comprising triethoxysilyl and pi-allyl based on biphenyl
(OEt)3: pi-allyl=1:5)
Add to 500 milliliters of flasks and the cyclohexyl biphenyl oxide (structural formula 3) with pi-allyl of mixing 35.98g,
The triethoxysilane of 14.03 milliliters, the platinum oxide of 216 milligrams and the toluene of 100 milliliters, stir the most under argon gas at 85 DEG C
Mix 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxidation
Thing.The NMR data of gained end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 1.6H), 1.20 (t, J=7.0Hz, 7.2H), 1.62-
1.72 (m, 1.6H), 2.61 (t, J=7.6Hz, 1.6H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=4.2Hz, 2H),
3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 4.8H), 3.97 (dd, J=5.2Hz, 2H), 4.14 (dd,
J=3.2Hz, 2H), 4.93-5.01 (m, 2.4H), 5.80-5.95 (m, 1.2H), 6.87-7.04 (m, 6H).
Synthetic example 20: synthesize the epoxide (Si comprising triethoxysilyl and pi-allyl based on biphenyl
(OEt)3: pi-allyl=1:0.33)
Add to 500 milliliters of flasks and the mixing cyclohexyl biphenyl oxide (structural formula 3) with pi-allyl of 8.20g, 5.99
Triethoxysilane, the platinum oxide of 98 milligrams and the toluene of 100 milliliters of milliliter, stirs 24 little the most under argon gas at 85 DEG C
Time.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxide.Institute
The NMR data obtaining end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 3H), 1.20 (t, J=7.0Hz, 13.5H), 1.62-
1.72 (m, 3H), 2.61 (t, J=7.6Hz, 3H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=4.2Hz, 2H),
3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 9H), 3.97 (dd, J=5.2Hz, 2H), 4.14 (dd, J
=3.2Hz, 2H), 4.93-5.01 (m, 1H), 5.80-5.95 (m, 0.5H), 6.87-7.04 (m, 6H).
Synthetic example 21: synthesize the epoxide (Si comprising methoxysilyl and pi-allyl based on biphenyl
(OMe)3: pi-allyl=1:9)
Add to 500 milliliters of flasks and the mixing cyclohexyl biphenyl oxide (structural formula 3) with pi-allyl of 10.26g, 0.78
Trimethoxy silane, the platinum oxide of 62 milligrams and the toluene of 100 milliliters of milliliter, stirs 24 little the most under argon gas at 85 DEG C
Time.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxide.Institute
The NMR data obtaining end product is as follows.
1H NMR (400MHz, DMSO): δ=0.54 (t, J=8.0Hz, 0.4H), 1.55 (m, 0.4H), 2.49-2.51
(m, 0.4H), 2.70 (dd, J=2.6Hz, 2H), 2.82 (dd, J=4.2Hz, 2H), 3.26-3.32 (m, 5.4H), 3.42 (s,
1.8H), 3.84 (dd, J=5.4Hz, 2H), 4.26 (dd, J=3.2Hz, 2H), 4.94-5.01 (m, 3.6H), 5.83-5.95
(m,1.8H),6.83-7.02(m,6H)。
Synthetic example 22: synthesize the epoxide (Si comprising triethoxysilyl and pi-allyl based on benzene
(OEt)3: pi-allyl=1:3)
Add to 500 milliliters of flasks and the mixing phenyl ring thing (structural formula 4) with pi-allyl of 10g, 3.36 millis
Triethoxysilane, the platinum oxide of 75 milligrams and the toluene of 100 milliliters risen, stirs 24 little the most under argon gas at 85 DEG C
Time.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxide.Institute
The NMR data obtaining end product is as follows.
[structural formula 4]
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 1H), 1.20 (t, J=7.0Hz, 4.5H), 1.62-
1.72 (m, 1H), 2.61 (t, J=7.6Hz, 1H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=4.2Hz, 2H),
3.11-3.35 (m, 5H), 3.79 (dt, J=19.2,5.2,1.6Hz, 3H), 3.97 (dd, J=5.2Hz, 2H), 4.14 (dd, J
=3.2Hz, 2H), 4.97-5.03 (m, 3H), 5.93-6.03 (m, 1.5H), 6.68 (s, 1H), 6.72 (s, 1H).
Synthetic example 23: synthesize the epoxide (Si comprising triethoxysilyl and pi-allyl based on fluorenes
(OEt)3: pi-allyl=1:3)
Add to 500 milliliters of flasks and the mixing fluorenyl epoxide (structural formula 5) with pi-allyl of 10g, 1.87 millis
Triethoxysilane, the platinum oxide of 42 milligrams and the toluene of 100 milliliters risen, stirs 24 little the most under argon gas at 85 DEG C
Time.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxide.Institute
The NMR data obtaining end product is as follows.
[structural formula 5]
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 1H), 1.20 (t, J=7.0Hz, 4.5H), 1.62-
1.72 (m, 1H), 2.61 (t, J=7.6Hz, 1H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=4.2Hz, 2H),
3.11-3.35 (m, 5H), 3.79 (dt, J=19.2,5.2,1.6Hz, 3H), 3.97 (dd, J=5.2Hz, 2H), 4.14 (dd, J
=3.2Hz, 2H), 4.97-5.03 (m, 3H), 5.93-6.03 (m, 1.5H), 6.70 (d, J=7.6Hz, 2H), 6.94 (dd, J=
2.8Hz, 2H), 6.99 (d, J=7.6Hz, 2H), 7.22-7.36 (m, 6H), 7.74 (d, J=7.2Hz, 2H).
Synthetic example 24: synthesize the epoxy compound comprising triethoxysilyl and pi-allyl based on tetraphenylmethane
Thing (Si (OEt)3: pi-allyl=1:3)
Add to 500 milliliters of flasks and the epoxide (structure based on tetraphenylmethane with pi-allyl of mixing 10g
Formula 6), the triethoxysilane of 1.86 milliliters, the platinum oxide of 42 milligrams and the toluene of 100 milliliters, the most under argon gas in 85 DEG C
Lower stirring 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain terminal ring
Oxide.The NMR data of gained end product is as follows.
[structural formula 6]
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 1H), 1.20 (t, J=7.0Hz, 4.5H), 1.62-
1.72 (m, 1H), 2.61 (t, J=7.6Hz, 1H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=4.2Hz, 2H),
3.11-3.35 (m, 5H), 3.79 (dt, J=19.2,5.2,1.6Hz, 3H), 3.97 (dd, J=5.2Hz, 2H), 4.14 (dd, J
=3.2Hz, 2H), 4.97-5.03 (m, 3H), 5.93-6.03 (m, 1.5H), 6.71-6.99 (m, 8H), 7.14-7.26 (m,
6H)。
Synthetic example 25: synthesize the epoxy compound comprising triethoxysilyl and pi-allyl based on tetraphenyl ethane
Thing (Si (OEt)3: pi-allyl=1:1)
Add to 500 milliliters of flasks and the epoxide (structure based on tetraphenyl ethane with pi-allyl of mixing 10g
Formula 7), the triethoxysilane of 2.80g, the platinum oxide of 77 milligrams and the toluene of 100 milliliters, stir at 85 DEG C the most under argon gas
Mix 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxidation
Thing.The NMR data of gained end product is as follows.
[structural formula 7]
1H NMR (400MHz, DMSO): δ=6.98-6.87 (m, 8H), 6.66-6.55 (m, 8H), 5.94-5.82 (m,
1H),5.28-5.11(m,2H),4.54(br.s,2H),4.47-4.43(m,2H),4.11-4.05(m,2H),3.84-3.80
(m,8H),3.29-3.25(m,4H),2.86-2.83(m,2H),2.69-2.67(m,2H),1.80-1.70(m,2H),1.22
(t, 9H, J=7.2Hz), 0.67-0.60 (m, 2H).
Synthetic example 26: synthesize the ring comprising triethoxysilyl and ethyl silicane base based on tetraphenyl ethane
Oxygen compound (Si (OEt)3:Si(Et)3=1:1)
Add to 500 milliliters of flasks and the epoxide (structural formula based on tetraphenyl ethane with hydroxyl of mixing 10g
8), the diisopropylethylamine (DIPEA) of 5.10g, the triethoxysilylpropyltetrasulfide isocyanates of 5.9g
(triethoxysilyl propylisocyanate), the trimethylsilylpropyl isocyanates of 3.92g
(trimethylsilyl propylisocyanate) and the oxolane (THF) of 200 milliliters, the most under argon gas in 60 DEG C
Lower stirring 12 hours.After reacting, ethyl acetate (EA) and H are used2O reaction mixture.Separate organic layer, to organic
MgSO is added in Ceng4, thus remove remaining H2O.Filter reactant mixture with diatomaceous earth filter, use evaporimeter to remove molten
Agent, obtains final epoxide.The NMR data of gained end product is as follows.
[structural formula 8]
1H NMR (400MHz, DMSO): δ=7.31-7.11 (m, 12H), 6.68-6.55 (m, 4H), 5.32 (t, 2H,
6.0Hz),4.54(s,2H),4.08-4.04(m,2H),3.83-3.77(m,8H),3.36-3.32(m,4H),3.25-3.23
(m, 2H), 2.88-2.81 (m, 2H), 2.67-2.65 (m, 2H), 1.74-1.66 (m, 4H), 1.24 (t, 9H, J=7.2Hz),
0.84-0.58(m,19H)。
Synthetic example 27: synthesize and based on double naphthalenes (bisnaphthalene) comprise triethoxysilyl and pi-allyl
Epoxide (Si (OEt)3: pi-allyl=1:1)
Add to 500 milliliters of flasks and the epoxide based on double naphthalenes (structural formula 9) with pi-allyl of mixing 10g,
The triethoxysilane of 3.13g, the platinum oxide of 87 milligrams and the toluene of 100 milliliters, stir 24 the most under argon gas at 85 DEG C
Hour.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxide.
The NMR data of gained end product is as follows.
[structural formula 9]
1H NMR (400MHz, DMSO): δ=7.78-7.66 (m, 4H), 7.34-7.25 (m, 4H), 6.92-6.89 (m,
2H),5.96-5.80(m,1H),5.30-5.10(m,2H),4.75(s,2H),4.49(m,2H),4.12-4.06(m,2H),
3.84-3.78(m,8H),3.31-3.25(m,2H),2.89-2.83(m,4H),2.69-2.64(m,2H),1.75-1.70(m,
2), 1.22 (t, 9H, J=7.2Hz), 0.67-0.60 (m, 2H).
Synthetic example 28: synthesize the epoxy compounds comprising triethoxysilyl and ethyl silicane base based on double naphthalenes
Thing (Si (OEt)3:Si(Et)3=1:1)
Add to 500 milliliters of flasks and the epoxide based on double naphthalenes (structural formula 10) with hydroxyl of mixing 10g,
The diisopropylethylamine (DIPEA) of 5.82g, the triethoxysilylpropyltetrasulfide isocyanates of 6.7g, the trimethyl first of 4.49g
Ethoxysilylpropyl isocyanates and the oxolane (THF) of 200 milliliters, stir 12 hours the most under argon gas at 60 DEG C.?
After reaction, use ethyl acetate (EA) and H2O reaction mixture.Separate organic layer, in organic layer, add MgSO4, by
This removes remaining H2O.Filter reactant mixture with diatomaceous earth filter, use evaporimeter to remove solvent, obtain final epoxy
Compound.The NMR data of gained end product is as follows.
[structural formula 10]
1H NMR (400MHz, DMSO): δ=7.78-7.66 (m, 4H), 7.34-7.25 (m, 4H), 6.92-6.89 (m,
2H),4.75(s,2H),4.12-4.06(m,2H),3.84-3.78(m,8H),3.36-3.25(m,6H),2.89-2.83(m,
2H), 2.69-2.64 (m, 2H), 1.75-1.70 (m, 4H), 1.22 (t, 9H, J=7.2Hz), 0.88-0.57 (m, 19H).
Synthetic example 29: synthesize the epoxidation comprising triethoxysilyl and pi-allyl based on phenol novolacs
Compound (Si (OEt)3: pi-allyl=1:1)
The phenol Novolac epoxy compound (structural formula 11) with pi-allyl of 10g, the oxygen of 98 milligrams is added to flask
Change platinum, the triethoxysilane of 3.57g and the toluene of 150 milliliters, be then stirred at room temperature 5 minutes.Then, reaction is mixed
Thing heats at 85 DEG C and stirs 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove molten
Agent obtains final epoxide, and wherein the concentration ratio of epoxide group and triethoxysilyl and pi-allyl is 1:1:1.Institute
The NMR data obtaining end product is as follows.
[structural formula 11]
1H NMR(400MHz,CDCl3): δ=7.15-6.70 (m, 21.68H), 6.04-6.00 (m, 2.21H), 5.41-
5.20(m,4.65H),4.49-4.47(m,4.58H),4.20-3.79(m,32.48H),3.33-3.25(m,2.35H),2.73-
2.59(m,5.99H),1.82-1.70(m,4.48H),1.24-1.20(m,18.75H),0.80-0.61(m,4.16H)。
Synthetic example 30: synthesize the epoxidation comprising triethoxysilyl and pi-allyl based on cresol novolak
Compound (Si (OEt)3: pi-allyl=1:1)
The cresol novolak epoxy compound (structural formula 12) with pi-allyl of 10g, the oxygen of 92 milligrams is added to flask
Change platinum, the triethoxysilane of 4.00g and the toluene of 150 milliliters, be then stirred at room temperature 5 minutes.Then, reaction is mixed
Thing heats at 85 DEG C and stirs 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove molten
Agent obtains final epoxide, and wherein the concentration ratio of epoxide group and triethoxysilyl and pi-allyl is 1:1:1.Institute
The NMR data obtaining end product is as follows.
[structural formula 12]
1H NMR (400MHz, DMSO): δ=7.02-6.89 (m, 10H), 6.05-6.01 (m, 1.43H), 5.43-5.20
(m,3.04H),4.50-4.46(m,3.28H),4.24-3.36(m,23.4H),3.34-3.19(m,1.55H),2.84-2.52
(m,3.7H),2.24-2.10(m,12.3H),1.83-1.70(m,2.74H),1.24-1.20(m,12.11H),0.80-0.61
(m,2.53H)。
Synthetic example 31: synthesize the epoxidations comprising triethoxysilyl and pi-allyl based on bis-phenol novolaks
Compound (Si (OEt)3: pi-allyl=1:1)
The bis-phenol novolak epoxides (structural formula 13) with pi-allyl of 10g, the oxygen of 92 milligrams is added to flask
Change platinum, the triethoxysilane of 4.0g and the toluene of 150 milliliters, be thus stirred at room temperature 5 minutes.Then, reaction is mixed
Thing heats at 85 DEG C and stirs 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove molten
Agent obtains final epoxide, and wherein the concentration ratio of epoxide group and triethoxysilyl and pi-allyl is 1:1:1.Institute
The NMR data obtaining end product is as follows.
[structural formula 13]
1H NMR (400MHz, DMSO): δ=7.32-7.24 (m, 12H), 6.75-6.65 (m, 20H), 6.06-6.15 (m,
1.72H),5.42-5.22(m,3.54H),4.51-4.47(m,3.91H),4.22-3.79(m,42.14H),3.36-3.28(m,
15.01H),2.77-2.58(m,14.55H),1.83-1.69(m,3.55H),1.62(m,32.9H),1.27-1.20(m,
17.04H),0.83-0.62(m,3.12H)。
Synthetic example 32: synthesize the epoxy compound comprising triethoxysilyl and pi-allyl based on naphthol novolak varnish
Thing (Si (OEt)3: pi-allyl=1:1)
To flask add 10g there is the naphthol novolak novalac epoxy compound (structural formula 14) of pi-allyl, the oxidation of 82 milligrams
Platinum, the triethoxysilane of 3.56g and the toluene of 150 milliliters, be then stirred at room temperature 5 minutes.Then, by reactant mixture
Heat at 85 DEG C and stir 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent
Obtaining final epoxide, wherein the concentration ratio of epoxide group and triethoxysilyl and pi-allyl is 1:1:1.Gained
The NMR data of end product is as follows.
[structural formula 14]
1H NMR (400MHz, DMSO): δ=8.03-8.02 (m, 1.27H), 7.88-7.51 (m, 9.99H), 7.39-
7.02(m,10.43H),6.59-6.54(m,4.41H),6.05-6.01(m,1.17H),5.40-5.20(m,2.45H),4.50-
4.46(m,2.47H),4.42H(s,3.84H),4.21-3.80(m,15.4H),3.35-3.25(m,7.2H),2.74-2.59
(m,9.8H),1.83-1.69(m,1.22H),1.25-1.21(m,5.97H),0.80-0.61(m,1.09H)。
Synthetic example 33: synthesize triethoxysilyl and the pi-allyl of comprising based on dianil (bisaniline)
Epoxide (Si (OEt)3: pi-allyl=1:1)
To flask add 20g there is the epoxide based on dianil (structural formula 15) of pi-allyl, the oxidation of 0.12g
Platinum (PtO2), the triethoxysilane of 9.7g and the toluene of 250 milliliters, be thus stirred at room temperature 5 minutes.Then, will reaction
Mixture heats at 85 DEG C and stirs 12 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove
Going solvent to obtain final epoxide, wherein the concentration ratio of epoxide group and triethoxysilyl and pi-allyl is 2:1:
1.The NMR data of gained end product is as follows.
[structural formula 15]
1H NMR(400MHz,CDCl3): δ=7.12-7.08 (m, 4H), 6.77-6.74 (m, 4H), 5.93-5.80 (m,
1.01H), 5.48-5.30 (m, 2.11H), 3.84 (q, 6.06H, J=6.8Hz), 3.82 (s, 2H), 3.76-3.62 (m,
4.25H),3.49-3.40(m,1.8H),3.22-3.16(m,3.99H),2.81-2.78(m,1.8H),2.60-2.58(m,
1.8H), 1.80-1.70 (m, 2.01H), 1.22 (t, 8.82H, J=7.2Hz), 0.67-0.60 (m, 1.79H).
Synthetic example 34: synthesize the epoxide (Si comprising triethoxysilyl and pi-allyl based on diamidogen
(OEt)3: pi-allyl=1:1)
To flask add 10g there is the epoxide based on diamidogen (structural formula 16) of pi-allyl, the platinum oxide of 0.14g
(PtO2), the triethoxysilane of 12.0g and the toluene of 250 milliliters, be then stirred at room temperature 5 minutes.Then, reaction is mixed
Compound heats at 80 DEG C and stirs 12 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove
Solvent obtains final epoxide, and wherein the concentration ratio of epoxide group and triethoxysilyl and pi-allyl is 2:1:1.
The NMR data of gained end product is as follows.
[structural formula 16]
1H NMR(400MHz,CDCl3): δ=7.41-7.09 (m, 4H), 5.93-5.80 (m, 1H), 5.44-5.21 (m,
2H),3.84-3.54(m,12H),3.25-3.11(m,2H),2.85-2.42(m,10H),1.81-1.69(m,2H),1.22(t,
9H, J=7.2Hz), 0.66-0.60 (m, 2H).
Contrast synthetic example 1: synthesize the epoxide (Si comprising triethoxysilyl based on bisphenol-A
(OEt)3:Si(Et)3: pi-allyl=1:0:0)
Add to 500 milliliters of flasks and the bisphenol A epoxide (structural formula 1) with pi-allyl of mixing 26.25g,
The triethoxysilane of 25.35 milliliters, the platinum oxide of 250 milligrams and the toluene of 200 milliliters, stir the most under argon gas at 85 DEG C
Mix 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxidation
Thing.The NMR data of gained end product is as follows.
[structural formula 1]
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 4H), 1.20 (t, J=7.0Hz, 18H), 1.60 (s,
6H), 1.62-1.72 (m, 4H), 2.61 (t, J=7.6Hz, 4H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=
4.2Hz, 2H), 3.30-3.34 (m, 2H), 3.79 (dt, J=19.2,5.2,1.6Hz, 12H), 3.97 (dd, J=5.2Hz,
2H), 4.14 (dd, J=3.2Hz, 2H), 6.70 (d, J=7.6Hz, 2H), 6.94 (dd, J=2.8Hz, 2H), 6.99 (d, J=
7.6Hz,2H)。
Contrast synthetic example 2: synthesize the epoxide (Si comprising methoxysilyl based on bisphenol-A
(OMe)3:Si(Me)3: pi-allyl=1:0:0)
Add to 500 milliliters of flasks and the bisphenol A epoxide (structural formula 1) with pi-allyl of mixing 17.28g,
The trimethoxy silane of 31.38 milliliters, the platinum oxide of 279 milligrams and the toluene of 150 milliliters, stir the most under argon gas at 85 DEG C
Mix 24 hours.After reacting, filter gained crude product with kieselguhr, use evaporimeter to remove solvent and obtain final epoxidation
Thing.The NMR data of gained end product is as follows.
1H NMR(400MHz,CDCl3): δ=0.64-0.69 (m, 4H), 1.60 (s, 6H), 1.62-1.72 (m, 4H),
2.61 (t, J=7.6Hz, 4H), 2.74 (dd, J=2.6Hz, 2H), 2.86 (dd, J=4.2Hz, 2H), 3.30-3.34 (m,
2H), 3.45 (s, 9H), 3.97 (dd, J=5.2Hz, 2H), 4.14 (dd, J=3.2Hz, 2H), 6.70 (d, J=7.6Hz, 2H),
6.94 (dd, J=2.8Hz, 2H), 6.99 (d, J=7.6Hz, 2H).
Evaluation of physical properties: manufacture cured product and assessment heating resistance property
1. prepare epoxy resin composite material
(1) epoxy resin fiberglass composite (cured product) is prepared
According to the formula shown in table 1, by epoxide, silica slurry, (solid content is 70 weight %, 2-methoxyl group
Ethanol, average silica size is 1 micron) and Pioloform, polyvinyl acetal be dissolved in methyl ethyl ketone.Solid content is 40 weights
Amount %.After mixture is stirred 1 hour at 1500 rpm, firming agent is added to mixed solution, and remixes 50
Minute.Glass fibre (Dong Fang company (Nittobo Co.), glass fiber cloth T-glass fibre) is impregnated into described ring
Epoxy resins mixture, to prepare glass fiber compound material.Then, composite is put into it is heated to the vacuum drying oven of 100 DEG C
In, and remove solvent, and then solidifying in hot press, described hot press is preheating to 120 DEG C, solidifies 2 hours at 120 DEG C,
At 180 DEG C solidify 2 hours, at a temperature of ＞ 200 DEG C solidify 2 hours, be derived from glass fiber compound material film (4mm ×
16mm×0.1mm).When preparing composite material film, regulate composite material film according to the pressure of press and the viscosity of resin
Resin content in resin content, and composite material film is as shown in table 1.
(2) epoxy filler composite (cured product) is prepared
According to the formula shown in table 2, by epoxide, silica slurry, (solid content is 70 weight %, 2-methoxyl group
Ethanol, average silica granularity is 1 micron) and Pioloform, polyvinyl acetal be dissolved in methyl ethyl ketone.Solid content is 40 weights
Amount %.After mixture is stirred 1 hour at 1500 rpm, firming agent is added to mixed solution, and remixes 50
Minute.Then, this mixture is put in the vacuum drying oven being heated to 100 DEG C, and remove solvent, then solid in hot press
Changing, described hot press is preheating to 120 DEG C, solidifies 2 hours at 120 DEG C, solidifies 2 hours, in the temperature of ＞ 200 DEG C at 180 DEG C
The lower solidification of degree 2 hours, is derived from epoxy filler (inorganic particle) composite (5mm × 5mm × 5mm).
2. characterize thermostability
Become by the size using thermomechanical analyzer to measure the cured product obtained in the embodiment of Tables 1 and 2
Change the relation with temperature, and be shown in Tables 1 and 2.The sample of epoxy resin fiberglass composite material film is prepared as 4 × 16 ×
0.1(mm3) size, the sample of filler composite materials is prepared as 5 × 5 × 3 (mm3) size.
[table 1-1] epoxy resin fiberglass composite
[table 1-2] epoxy resin fiberglass composite
[table 1-3] epoxy resin fiberglass composite
[table 1-4] epoxy resin fiberglass composite
[table 2-1] filler composite materials
[table 2-2] filler composite materials
* annotation: compound used in table 1 and 2 is as follows.
(1) diglycidyl ether (Mw=377, aldrich company (Aldrich Co.)) of DGEBA: bisphenol-A
(2) EXA4700: epoxide based on double naphthalenes (EEW=162)
(3) YX4000H: epoxide based on biphenyl
(4): the epoxy resin (Stulak torr company (Strruktol Co)) of modified rubber
(5) HF-1M: phenol novolacs base firming agent (transparent tile Plastics Industry Company (Meiwa Plastic
Industries), HEW=107)
(6) TPP: triphenylphosphine (aldrich company)
(7) 2E4MZ:2-ethyl-4-methylimidazole (aldrich company)
As shown in Tables 1 and 2, with the glass fibre prepared according to the epoxide of the illustrative embodiments in the present invention
Composite and silicon dioxide composite material present low CTE, and do not present glass transition temperature (without Tg's), thus improve resistance to
Hot.Additionally, because introducing non-reacted functional group, improving and using the epoxy according to the illustrative embodiments in the present invention
The fragility of composite prepared by compound.As it is shown in figure 1, only have the epoxide (contrast of triethoxysilyl
Synthetic example 1) glass fiber compound material sample surfaces in observe crackle.As a comparison, there is pi-allyl at the same time
In the case of the epoxide (synthetic example 4) of triethoxysilyl, at the glass fiber compound material table of solidification
Face is not observed crackle.
As in figure 2 it is shown, in the situation of the epoxide (contrast synthetic example 2) only with methoxysilyl
Under, solidification rate is significantly very fast, and gained sample is notable fragility, therefore cannot prepare the glass fibers that can be used as test sample
Dimension composite.But, in the case of there is the epoxide of methoxysilyl and pi-allyl at the same time, cured product
Fragility improved (Fig. 2 B), therefore, measurable glass fiber compound material can be prepared, and even at the table of cured product
Face is not observed crackle.
Claims (41)
1. an epoxide, comprising:
In core,
I) selected from least two epoxide group of following general formula E 1 and E2 epoxide group；
Ii) selected from least one alkoxysilyl of lower group: following formula A1 to A5；With
Iii) selected from least one non-reacted silicyl, thiazolinyl or a combination thereof of lower group: following formula A6 to A10,
[general formula E 1]
[general formula E 2]
[formula A1]
-CRbRc-CHRa-CH2-SiR1R2R3
[formula A2]
-O-(CH2)m+2-SiR1R2R3
[formula A3]
-O-CONH(CH2)m-SiR1R2R3
[formula A4]
-(CH2)m+2-SiR1R2R3
[formula A5]
-CONH(CH2)m-SiR1R2R3
In formula A1, Ra, RbAnd RcIt is H or the alkyl with 1 to 6 carbon atoms, in formula A1 to A5, R independently1To R3
In at least one be the alkoxyl with 1 to 6 carbon atoms, and remaining R1 to R3 is the alkane with 1 to 10 carbon atoms
Base, wherein said alkyl and described alkoxyl are straight or brancheds, are ring-type or acyclic, and with or without N, O, S, or
P hetero atom, m is the integer of 1 to 10,
[formula A6]
-CRbRc-CHRa-CH2-SiR4R5R6
[formula A7]
-O-(CH2)m+2-SiR4R5R6
[formula A8]
-O-CONH(CH2)m-SiR4R5R6
[formula A9]
-(CH2)m+2-SiR4R5R6
[formula A10]
-CONH(CH2)m-SiR4R5R6
In formula A6, Ra,RbAnd RCIt is H or the alkyl with 1 to 6 carbon atoms independently, in above-mentioned formula A6 to A10,
R4To R6It is that there is the aliphatic of 1 to 20 carbon atoms, the alicyclic or non-reacted group of aryl moieties, wherein said non-
Reactive group is straight or branched, is ring-type or acyclic, and with or without N, O, S, or P hetero atom, m is 1 to 10
Integer.
2. epoxide as claimed in claim 1, it is characterised in that described thiazolinyl is selected from lower group: following formula A11 arrives
A13,
[formula A11]
-CRbRc-CRa=CH2
[formula A12]
-O-(CH2)m-CH=CH2
[formula A13]
-(CH2)m-CH=CH2
In formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein said alkyl is straight chain
Or side chain, it is ring-type or acyclic, and with or without N, O, S, or P hetero atom, the m in formula A12 and formula A13 is
The integer of 1 to 10.
3. epoxide as claimed in claim 1, it is characterised in that described core is selected from lower group: following formula AC to OC,
In above-mentioned general formula D C, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
In above-mentioned formula HC, J is to be directly connected to group ,-CH2-, or
Wherein, Rx is H or C1-C3Alkyl,
In above-mentioned formula IC, K is selected from the one of lower group: following formula 1ac to 1fc,
In above-mentioned formula LC, L is
AndIn, Ry is straight or branched C1-C10 alkyl,
In above-mentioned formula M C, M is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, orAnd R is H or C1-C3 alkyl,
In above-mentioned formula IC, when K is 1ac to 1ec, n is the integer of 3 or bigger, and when K is 1fc, n is the whole of two or more
Number, in above-mentioned formula JC, n is the integer of two or more, and in above-mentioned formula KC, n is the integer of 0 or bigger, at above-mentioned formula
In LC, when L isTime, n is 3 or bigger
Integer, and when L isTime, n is the integer of two or more.
4. epoxide as claimed in claim 3, it is characterised in that when selected from above-mentioned formula AC to HC and formula M C to OC
The core of same type when being two or more, the core of above-mentioned formula AC to HC is connected by following linking group LG1, and
The core of above-mentioned formula M C to OC is connected by following linking group LG2, [formula LG1]
[formula LG2]
5. epoxide as claimed in claim 1, it is characterised in that described epoxide passes through following formula AF to OF
In any one represent,
At least two in the substituent A of above-mentioned formula AF to FF is selected from following general formula E 1 and E2, at least one in substituent A
Selected from lower group: following formula A1 to A3, and remaining substituent A is independently selected from lower group: above-mentioned formula A6 to A8, formula A11,
Formula A12, and hydrogen,
At least two in the substituent A of above-mentioned formula GF to LF is represented by following general formula E 1, at least in substituent A
Individual represented by following formula A2 or formula A3, and remaining substituent A is independently selected from lower group: following formula A7, following
Formula A8, following formula A12, and hydrogen,
At least two in the substituent A of above-mentioned formula M F to OF is represented by following general formula E 2, at least in substituent A
Individual selected from following formula A4 and A5, and remaining substituent A is independently selected from lower group: following formula A9, following formula A10, under
State formula A13, and hydrogen,
In above-mentioned general formula D F, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
In above-mentioned formula HF, J is to be directly connected to group ,-CH2-orWherein Rx is H or C1-C3Alkyl,
In above-mentioned formula IF, K is the one selected from lower group: following formula 1A to 1F,
In above-mentioned formula LF, L is
Above-mentionedIn, Ry is straight or branched C1-C10 alkyl,
In above-mentioned formula M F, M is CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, orAnd R is H or C1-C3Alkyl,
In above-mentioned formula IF, when K is 1A to 1E, n is the integer of 3 or bigger, and when K is 1F, n is the whole of two or more
Number,
In above-mentioned formula JF, n is the integer of two or more,
In above-mentioned formula KF, n is the integer of 0 or bigger,
In above-mentioned formula LF, when L isTime,
N is the integer of 3 or bigger, and
When L isTime, n is the integer of two or more, and
In above-mentioned formula LF, p is 1 or 2,
[general formula E 1]
[general formula E 2]
[formula A1]
-CRbRc-CHRa-CH2-SiR1R2R3
[formula A2]
-O-(CH2)m+2-SiR1R2R3
[formula A3]
-O-CONH(CH2)m-SiR1R2R3
[formula A4]
-(CH2)m+2-SiR1R2R3
[formula A5]
-CONH(CH2)m-SiR1R2R3
In formula A1, Ra,RbAnd RcIt is H or the alkyl with 1 to 6 carbon atoms independently, in above-mentioned formula A1 to A5, R1
To R3In at least one be the alkoxyl with 1 to 6 carbon atoms, and remaining R1To R3There are 1 to 10 carbon atoms
Alkyl, wherein said alkyl and described alkoxyl are straight or brancheds, are ring-type or acyclic, and with or without N, O, S,
Or P hetero atom, m is the integer of 1 to 10,
[formula A6]
-CRbRc-CHRa-CH2-SiR4R5R6
[formula A7]
-O-(CH2)m+2-SiR4R5R6
[formula A8]
-O-CONH(CH2)m-SiR4R5R6
[formula A9]
-(CH2)m+2-SiR4R5R6
[formula A10]
-CONH(CH2)m-SiR4R5R6
In above-mentioned formula A6, Ra,RbAnd RcIt is H or the alkyl with 1 to 6 carbon atoms independently, arrives at above-mentioned formula A6
In A10, R4To R6It is that there is the aliphatic of 1 to 20 carbon atoms, alicyclic, the non-reacted group of aryl moieties, Qi Zhongsuo
Stating non-reacted group is straight or branched, is ring-type or acyclic, and with or without N, O, S, or P hetero atom, m is 1
To the integer of 10,
[formula A11]
-CRbRc-CRa=CH2
[formula A12]
-O-(CH2)m-CH=CH2
[formula A13]
-(CH2)m-CH=CH2
In formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein said alkyl is straight chain
Or side chain, it is ring-type or acyclic, and with or without N, O, S, or P hetero atom, the m in formula A12 and formula A13 is
The integer of 1 to 10.
6. epoxide as claimed in claim 1, it is characterised in that described epoxide comprises in core:
I) at least two epoxide group represented by following general formula E 1,
[general formula E 1]
Ii) at least one alkoxysilyl, it is represented by following formula A1
[formula A1]
-CRbRc-CHRa-CH2-SiR1R2R3
In formula A1, Ra,RbAnd RcIt is H or the alkyl with 1 to 6 carbon atoms independently, R1To R3In at least one be
There is the alkoxyl of 1 to 6 carbon atoms, and remaining R1To R3It is the alkyl with 1 to 10 carbon atoms, wherein said alkyl
Being straight or branched with described alkoxyl, be ring-type or acyclic, and with or without N, O, S, or P hetero atom, m is 1 to arrive
The integer of 10；And
Iii) at least one thiazolinyl, it is represented by following formula A11
[formula A11]
-CRbRc-CRa=CH2
In formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein said alkyl is straight chain
Or side chain, it is ring-type or acyclic, and with or without N, O, S, or P hetero atom.
7. epoxide as claimed in claim 1, it is characterised in that the alkoxyl represented by above-mentioned formula A1 to A5
R in silicyl1To R3In at least one be the alkoxyl with 2 to 4 carbon atoms.
8. epoxide as claimed in claim 1, it is characterised in that the alkoxyl represented by above-mentioned formula A1 to A5
R in silicyl1To R3It is entirely ethyoxyl.
9. epoxide as claimed in claim 1, it is characterised in that the alkoxyl represented by above-mentioned formula A1 to A5
R in silicyl1To R3Being entirely methoxyl group, described epoxide comprises at least one thiazolinyl.
10. a mixture for epoxide, it comprises epoxide as claimed in any one of claims 1-9 wherein, its
In when epoxide comprises non-reacted silicyl, described alkoxysilyl and described non-reacted silicyl
Ratio be within the scope of 1:99 to 99:1.
Preparing for 11. 1 kinds and have the method for the epoxide of any one in following formula AF to OF, described method is included in deposits
Under conditions of platinum catalyst and optional solvent, any one parent material and following formula in following formula AS1 to OS1
The reaction of the alkoxy silane of AS5, or parent material, there is the alkoxy silane of following formula AS5 and there is following formula
The reaction of the non-reacted silane of AS6,
[formula AS5]
HSiR1R2R3
In above-mentioned formula AS5, R1To R3In at least one be C1-C6 alkoxyl, preferably ethyoxyl, remaining R1To R3
Being C1-C10 alkyl, wherein said alkoxyl and described alkyl are straight or brancheds, are ring-type or acyclic, and have or do not have
There is N, O, S, or P hetero atom,
[formula AS6]
HSiR4R5R6
In above-mentioned formula AS6, R4To R6Be have the aliphatic of 1 to 20 carbon atoms, alicyclic, aryl moieties non-instead
Answering property group, wherein said non-reacted group is straight or branched, is ring-type or acyclic, and with or without N, O, S,
Or P hetero atom,
At least two in multiple substituent groups a1 of above-mentioned formula AS1 to FS1 is represented by following general formula E 1 or E2, described many
At least two in individual substituent group a1 is represented by following formula A11 or formula A12, and remaining multiple substituent group a1 is hydrogen,
At least two in substituent group a1 of above-mentioned formula GS1 to LS1 is represented, in substituent group a1 extremely by following general formula E 1
Few two are represented by following formula A12, and remaining substituent group a1 is hydrogen,
At least two in substituent group a1 of above-mentioned formula M S1 to OS1 is represented by above-mentioned general formula E 2, remaining substituent group a1
Represented by above-mentioned formula A13, and
In above-mentioned general formula D S1, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
In above-mentioned formula HS1, J is to be directly connected to group ,-CH2-, or
(Rx is H or C1-C3Alkyl),
In above-mentioned formula IS1, K is selected from the one of lower group: following formula 1a1 to 1f1,
In above-mentioned formula LS1, L is
?In, Ry is straight or branched C1-C10 alkyl,
In above-mentioned formula M S1, M is CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, orAnd R is H or C1-C3Alkyl,
In above-mentioned formula IS1, when K is 1a1 to 1e1, n is the integer of 3 or bigger, and when K is 1f1, n is two or more
Integer,
In above-mentioned formula JS1, n is the integer of two or more,
In above-mentioned formula KS1, n is the integer of 0 or bigger,
In above-mentioned formula LS1, when L isTime, n is
The integer of 3 or bigger, and when L is
Time, n is the integer of two or more, and
In above-mentioned formula LS1, p is 1 or 2,
[general formula E 1]
[general formula E 2]
[formula A11]
-CRbRc-CRa=CH2
[formula A12]
-O-(CH2)m-CH=CH2
[formula A13]
-(CH2)m-CH=CH2
In formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein said alkyl is straight chain
Or side chain, it is ring-type or acyclic, and with or without N, O, S, or P hetero atom, the m in formula A12 and formula A13 is
The integer of 1 to 10,
At least two in the substituent A of above-mentioned formula AF to FF is represented, in substituent A extremely by above-mentioned general formula E 1 or E2
Few one is selected from lower group: following formula A1 to A2, and remaining substituent A is independently selected from lower group: following formula A6, formula
A7, formula A11, formula A12, and hydrogen,
At least two in the substituent A of above-mentioned formula GF to LF is represented by following general formula E 1, at least in substituent A
Individual represented by following formula A2, and remaining substituent A be independently selected from lower group: following formula A7 and A12, and hydrogen,
At least two in the substituent A of above-mentioned formula M F to OF is represented by following general formula E 2, at least in substituent A
Individual represented by following formula A4, and remaining substituent A is independently selected from lower group: following formula A9 and formula A13, and
Hydrogen,
In above-mentioned general formula D F, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
In above-mentioned formula HF, J is to be directly connected to group ,-CH2-or(Rx is H or C1-C3Alkyl),
In above-mentioned formula IF, K is the one selected from lower group: following formula 1A to 1F,
In above-mentioned formula LF, L is
?In, Ry is straight or branched C1-C10 alkyl,
In above-mentioned formula M F, M is CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, orAnd R is H or C1-C3Alkyl,
In above-mentioned formula IF, when K is 1A to 1E, n is the integer of 3 or bigger, and when K is 1F, n is the whole of two or more
Number,
In above-mentioned formula JF, n is the integer of two or more,
In above-mentioned formula KF, n is the integer of 0 or bigger,
At above-mentioned formula LF, when L is
Time, n is the integer of 3 or bigger, and
When L is
Time, n is the integer of two or more, and
In above-mentioned formula LF, p is 1 or 2,
[general formula E 1]
[general formula E 2]
[formula A1]
-CRbRc-CHRa-CH2-SiR1R2R3
[formula A2]
-O-(CH2)m+2-SiR1R2R3
[formula A4]
-(CH2)m+2-SiR1R2R3
In formula A1, Ra,RbAnd RcIt is H or the alkyl with 1 to 6 carbon atoms independently, at above-mentioned formula A1, A2 and A4
In, R1To R3In at least one be the alkoxyl with 1 to 6 carbon atoms, and remaining R1To R3It is that there are 1 to 10 carbon
The alkyl of atom, wherein said alkyl and described alkoxyl are straight or brancheds, are ring-type or acyclic, and with or without
N, O, S, or P hetero atom, m is the integer of 1 to 10,
[formula A6]
-CRbRc-CHRa-CH2-SiR4R5R6
[formula A7]
-O-(CH2)m+2-SiR4R5R6
[formula A9]
-(CH2)m+2-SiR4R5R6
In above-mentioned formula A6, Ra,RbAnd RcIt is H or the alkyl with 1 to 6 carbon atoms independently, at above-mentioned formula A6, A7
With in A9, R4To R6It is to there is the aliphatic of 1 to 20 carbon atoms, alicyclic, the non-reacted group of aryl moieties, wherein
Described non-reacted group is straight or branched, is ring-type or acyclic, and with or without N, O, S, or P hetero atom, m is
The integer of 1 to 10,
[formula A11]
-CRbRc-CRa=CH2
[formula A12]
-O-(CH2)m-CH=CH2
[formula A13]
-(CH2)m-CH=CH2
In formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein said alkyl is straight chain
Or side chain, it is ring-type or acyclic, and with or without N, O, S, or P hetero atom, the m in formula A12 and formula A13 is
The integer of 1 to 10.
12. methods as claimed in claim 11, it is characterised in that described parent material and the alcoxyl with above-mentioned formula AS5
Base silane reacts to each other, thus relative to 1 equivalent thiazolinyl of parent material, the alkoxy silane with above-mentioned formula AS5 can be
Within 0.1 equivalent to 5 equivalent weight range.
13. methods as claimed in claim 11, it is characterised in that as whole R of the alkoxy silane with above-mentioned formula AS51
To R3When being methoxyl group, described alkoxy silane reacts with described parent material, thus relative to 1 equivalent alkene of parent material
Base, have the alkoxy silane of above-mentioned formula AS5 can be more than or equal to 0.1 equivalent and less than 1 equivalent weight range within.
Preparing for 14. 1 kinds and have the method for the epoxide of any one in following formula AF to OF, described method comprises:
Under conditions of there is optional solvent, there is in above-mentioned formula AS2 to OS2 the parent material of any one and have following
The reaction of the alkoxy silane of formula AS3, or parent material, there is the alkoxy silane of following formula AS3 and have following
The reaction of the non-reacted silane of formula AS4,
[formula AS3]
OCN-(CH2)m-SiR1R2R3
In above-mentioned formula AS3, R1To R3In at least one be C1-C6 alkoxyl, preferably ethyoxyl, remaining R1To R3
Being C1-C10 alkyl, wherein said alkoxyl and described alkyl are straight or brancheds, are ring-type or acyclic, and have or do not have
Having N, O, S, or P hetero atom, m is the integer of 1 to 10, the integer of preferably 3 to 6,
[formula AS4]
OCN-(CH2)m-SiR4R5R6
In above-mentioned formula AS4, R4To R6Be have the aliphatic of 1 to 20 carbon atoms, alicyclic, aryl moieties non-instead
Answering property group, wherein said non-reacted group is straight or branched, is ring-type or acyclic, and with or without N, O, S,
Or P hetero atom, and m is the integer of 1 to 10, the integer of preferably 3 to 6,
At least two in substituent group a2 of above-mentioned formula AS2 to FS2 is represented, in substituent group a2 extremely by following general formula E 2
Few two is hydroxyl, and remaining substituent group a2 is independently selected from lower group: hydrogen and following formula A11,
At least two in substituent group a2 of above-mentioned formula GS2 to LS2 is represented, in substituent group a2 extremely by above-mentioned general formula E 1
Few two is hydroxyl, and remaining substituent group a2 is hydrogen,
At least two in substituent group a2 of above-mentioned formula M S2 to OS2 is represented by above-mentioned general formula E 2, remaining substituent group a2
It is hydrogen,
In above-mentioned general formula D S2, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
In above-mentioned formula HS2, J is to be directly connected to group ,-CH2-, or
(Rx is H or C1-C3Alkyl),
In above-mentioned formula IS2, K is the one selected from lower group: following formula 1a2 to 1f2,
In above-mentioned formula LS2, L is
AndIn, Ry is straight or branched C1-C10 alkyl,
In above-mentioned formula M S2, M is CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, orAnd R is H or C1-C3Alkyl,
In above-mentioned formula IS2, when K is 2a to 2e, n is the integer of 3 or bigger, and when K is 2f, n is the whole of two or more
Number,
In above-mentioned formula JS2, n is the integer of two or more,
In above-mentioned formula KS2, n is the integer of 0 or bigger,
In above-mentioned formula LS2, when L is
Time, n is the integer of 3 or bigger, and when L is
Time, n is the integer of two or more, and
In above-mentioned formula LS2, p is 1 or 2,
[general formula E 1]
[general formula E 2]
[formula A11]
-CRbRc-CRa=CH2
In formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein said alkyl is straight chain
Or side chain, it is ring-type or acyclic, and with or without N, O, S, or P hetero atom,
At least two in the substituent A of above-mentioned formula AF to FF is represented by following general formula E 2, at least in substituent A
Individual represented by following formula A3, and remaining substituent A be independently selected from lower group: above-mentioned formula A8, following formula A11,
And hydrogen,
At least two in the substituent A of above-mentioned formula GF to LF is represented by following general formula E 1, at least in substituent A
Individual represented by following formula A3, and remaining substituent A be independently selected from following formula A8 and hydrogen,
At least two in the substituent A of above-mentioned formula M F to OF is represented by following general formula E 2, at least in substituent A
Individual represented by following formula A5, and remaining substituent A be independently selected from following formula A10 and hydrogen,
In above-mentioned general formula D F, I is-CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-,
In above-mentioned formula HF, J is to be directly connected to group ,-CH2-or(Rx is H or C1-C3Alkyl),
In above-mentioned formula IF, K is the one selected from lower group: following formula 1A to 1F,
In above-mentioned formula LF, L is
?In, Ry is straight or branched C1-C10 alkyl,
In above-mentioned formula M F, M is CH2-,-C(CH3)2-,-C(CF3)2-,-S-,-SO2-, orAnd R is H or C1-C3Alkyl,
In above-mentioned formula IF, when K is 1A to 1E, n is the integer of 3 or bigger, and when K is 1F, n is the whole of two or more
Number,
In above-mentioned formula JF, n is the integer of two or more,
In above-mentioned formula KF, n is the integer of 0 or bigger,
At above-mentioned formula LF, when L is
Time, n is the integer of 3 or bigger,
And when L is
Time, n is the integer of two or more, and
In above-mentioned formula LF, p is 1 or 2,
[general formula E 1]
[general formula E 2]
[formula A3]
-O-CONH(CH2)m-SiR1R2R3
[formula A5]
-CONH(CH2)m-SiR1R2R3
In above-mentioned formula A3 and A5, R1To R3In at least one be the alkoxyl with 1 to 6 carbon atoms, and remaining R1
To R3Being the alkyl with 1 to 10 carbon atoms, wherein said alkyl and described alkoxyl are straight or brancheds, are ring-type or nothing
Ring, and with or without N, O, S, or P hetero atom, and m is the integer of 1 to 10,
[formula A8]
-O-CONH(CH2)m-SiR4R5R6
[formula A10]
-CONH(CH2)m-SiR4R5R6
In above-mentioned formula A8 and A10, R4To R6It is that there is the aliphatic of 1 to 20 carbon atoms, alicyclic, aryl moieties
Non-reacted group, wherein said non-reacted group is straight or branched, is ring-type or acyclic, and with or without N,
O, S, or P hetero atom, and m is the integer of 1 to 10,
[formula A11]
-CRbRc-CRa=CH2
In formula A11, Ra,RbAnd RcBeing H or the alkyl with 1 to 6 carbon atoms independently, wherein said alkyl is straight chain
Or side chain, it is ring-type or acyclic, and with or without N, O, S, or P hetero atom.
15. methods as claimed in claim 14, it is characterised in that described parent material and the alcoxyl with above-mentioned formula AS3
Base silane reacts to each other, thus relative to 1 equivalent amido or hydroxyl of parent material, has the alkoxyl silicone of above-mentioned formula AS3
Alkane can be within 0.1 equivalent to 5 equivalent weight range.
16. methods as claimed in claim 14, it is characterised in that as whole R of the alkoxy silane with above-mentioned formula AS31
To R3When being methoxyl group, described parent material and the alkoxy silane with above-mentioned formula AS3 react to each other, thus relative to rising
1 equivalent amido or hydroxyl of beginning material, have the alkoxy silane of above-mentioned formula AS3 can be more than or equal to 0.1 equivalent and
Within 1 equivalent weight range.
17. 1 kinds of epoxy composites, it comprises epoxide as claimed in any one of claims 1-9 wherein.
18. 1 kinds of epoxy composites, it comprises epoxy mixture as claimed in claim 10.
19. epoxy composites as described in claim 17 or 18, it is characterised in that described epoxy composite also includes being selected from down
Group at least one epoxide: epoxide based on glycidyl ether, epoxide based on glycidyl,
Epoxide based on glycidyl amine, epoxide based on ethylene oxidic ester, rubber modified epoxy compound, based on
The epoxide of aliphatic polyglycidyl base and epoxide based on aliphatic glycidyl amine.
20. epoxy composites as claimed in claim 19, it is characterised in that described epoxide comprises double in nuclear structure
Phenol, biphenyl, naphthalene, benzene, dihydroxy diphenyl sulfide, fluorenes, anthracene, isocyanuric acid ester, triphenyl methane, 1,1,2,2-tetraphenyl ethane,
Tetraphenylmethane, 4,4'-MDA, amino-phenol, alicyclic compound, aliphatic compound or novolaks list
Unit.
21. epoxy composites as claimed in claim 19, it is characterised in that count on the basis of the gross weight of epoxide,
Described epoxy composite comprises 10 to 100 weight % and has the epoxide of alkoxysilyl, and 0 weight % is to 90 weights
Amount % is selected from least one epoxide of lower group: epoxide based on glycidyl ether, based on glycidyl
Epoxide, epoxide based on glycidyl amine, epoxide based on ethylene oxidic ester, rubber modified epoxy
Compound, epoxide based on aliphatic polyglycidyl base and epoxide based on aliphatic glycidyl amine.
22. epoxy composites as according to any one of claim 17-21, it is characterised in that described epoxy composite also wraps
Containing at least one filler selected from inorganic particle or fiber.
23. epoxy composites as claimed in claim 22, it is characterised in that described inorganic particle is at least selected from lower group
Kind: at least one metal-oxide selected from lower group: silicon dioxide, zirconium oxide, titanium oxide, aluminium oxide, silicon nitride, aluminium nitride and
Silsesquioxane.
24. epoxy composites as claimed in claim 22, it is characterised in that described fiber is selected from least one of lower group:
Glass fibre and organic fiber, described glass fibre is selected from E glass fibre, T glass fibre, S glass fibre, NE glass fibre, H
Glass fibre and quartz glass fibre；And described organic fiber is fine selected from liquid crystalline polyester fiber, polyethylene terephthalate
Dimension, full aromatics fiber, polybenzoxazole fibers, nylon fiber, PEN fiber, polypropylene fibre, polyether sulfone
Fiber, polyvinylidene fluoride fiber, polyethylene sulfide fiber and polyetheretherketonefiber fiber.
25. epoxy composites as claimed in claim 22, it is characterised in that when comprising described fiber, also comprise inorganic particulate
Grain.
26. 1 kinds of electronic materials, described electronic material comprises the epoxy composite as according to any one of claim 17-25.
27. 1 kinds of base materials, described base material comprises the epoxy composite as according to any one of claim 17-25.
28. 1 kinds of films, described film comprises the epoxy composite as according to any one of claim 17-25.
29. 1 kinds of laminates, described laminate is included in the epoxy composite used as according to any one of claim 17-25
The metal level on basal layer formed.
30. 1 kinds of printed circuit board (PCB)s, it includes laminate as claimed in claim 29.
31. 1 kinds of semiconductor devices, it includes the printed circuit board (PCB) described in claim 30.
32. 1 kinds of semiconductor sealing materials, it comprises the epoxy composite as according to any one of claim 17-25.
33. 1 kinds of semiconductor devices, it comprises the semiconductor sealing material described in claim 32.
34. 1 kinds of adhesive, described adhesive comprises the epoxy composite as according to any one of claim 17-25.
35. 1 kinds of paint, described paint comprises the epoxy composite as according to any one of claim 17-25.
36. a composite, described composite comprises the epoxy composite as according to any one of claim 17-25.
37. 1 kinds of pre impregnated materials, described pre impregnated material comprises the epoxy combination as according to any one of claim 13-25
Thing.
38. 1 kinds of laminates, described laminate is by arranging metal level on pre impregnated material as claimed in claim 37
There is provided.
39. 1 kinds of cured products, described cured product is consolidating of the epoxy composite as according to any one of claim 17-25
Change product.
40. cured products as claimed in claim 39, it is characterised in that there is the thermal expansion system less than or equal to 60ppm/ DEG C
Number.
41. cured products as claimed in claim 39, it is characterised in that there is the glass transition temperature higher than 100 DEG C, or
Person does not show glass transition temperature.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20140019179 | 2014-02-19 | ||
| KR10-2014-0019179 | 2014-02-19 | ||
| KR10-2014-0175937 | 2014-12-09 | ||
| KR1020140175937A KR101755323B1 (en) | 2014-02-19 | 2014-12-09 | New epoxy compound, mixture, composition, cured product thereof, preparing method thereof, and use thereof |
| PCT/KR2015/001605 WO2015126143A1 (en) | 2014-02-19 | 2015-02-17 | Novel epoxy compound, mixture, composition, and cured product comprising same, method for preparing same, and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106232608A true CN106232608A (en) | 2016-12-14 |
| CN106232608B CN106232608B (en) | 2020-03-17 |
Family
ID=54059955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580020302.8A Active CN106232608B (en) | 2014-02-19 | 2015-02-17 | Epoxy compound, mixture, composition and cured product containing the same, and preparation method and application thereof |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US10597412B2 (en) |
| JP (1) | JP6423443B2 (en) |
| KR (1) | KR101755323B1 (en) |
| CN (1) | CN106232608B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110121531A (en) * | 2016-12-28 | 2019-08-13 | 三菱瓦斯化学株式会社 | Resin composition for printed circuit board, prepreg, resin sheet, plywood, clad with metal foil plywood, printed circuit board and multilayer board |
| CN110139893A (en) * | 2016-12-28 | 2019-08-16 | 三菱瓦斯化学株式会社 | Prepreg, plywood, clad with metal foil plywood, printed circuit board and multilayer board |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170287838A1 (en) * | 2016-04-02 | 2017-10-05 | Intel Corporation | Electrical interconnect bridge |
| EP3348560A1 (en) * | 2017-01-16 | 2018-07-18 | Spago Nanomedical AB | Chemical compounds for coating of nanostructures |
| WO2018225880A1 (en) | 2017-06-05 | 2018-12-13 | 한국생산기술연구원 | Compound having alkoxysilyl group and active ester group, method for preparing same, composition including same, and use |
| JP6812315B2 (en) * | 2017-07-28 | 2021-01-13 | 上野製薬株式会社 | 6- (2-oxylanylmethoxy) -2-naphthoic acid alkenyl ester and its production method |
| KR101895323B1 (en) * | 2018-07-03 | 2018-09-05 | 주식회사 삼양사 | Epoxy compound using thiol-ene reaction and method for preparing the same, and composite of organic-inorganic materials comprising a cured product thereof and method for preparing the composite |
| KR102376880B1 (en) * | 2019-07-04 | 2022-03-21 | (주)이녹스첨단소재 | interlayer insulating material for printed wiring board, interlayer insulating film containing the same and manufacturing method thereof |
| KR102232340B1 (en) * | 2019-11-15 | 2021-03-26 | 한국생산기술연구원 | Composition of alkoxysilyl-functionalized epoxy resin and composite thereof |
| JP7479564B2 (en) | 2021-03-15 | 2024-05-08 | 三菱電機株式会社 | Adhesives, rotating electrical machines, electronic parts and aircraft |
| JP7378438B2 (en) * | 2021-03-31 | 2023-11-13 | 三菱電機株式会社 | Liquid thermosetting resin composition, method for curing liquid thermosetting resin composition, stator coil, and rotating electric machine |
| KR102673997B1 (en) | 2021-11-05 | 2024-06-13 | 한국생산기술연구원 | Epoxy resin, preparing method thereof, epoxy composition comprising the same, and ths use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336786A (en) * | 1992-12-07 | 1994-08-09 | Shin-Etsu Chemical Company, Limited | Organic silicon compounds |
| JPH06345847A (en) * | 1993-06-07 | 1994-12-20 | Shin Etsu Chem Co Ltd | Epoxy resin composition and semiconductor device |
| KR20130135733A (en) * | 2012-06-01 | 2013-12-11 | 한국생산기술연구원 | Composition and cured product comprising epoxy compound having alkoxysilyl group and inorganic particle, use thereof and preparing method of epoxy compound having alkoxysilyl group |
| WO2014042491A1 (en) * | 2012-09-17 | 2014-03-20 | 한국생산기술연구원 | Epoxy compound having alkoxysilyl group, method for preparing same, composition comprising same, cured product made therefrom, and use thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11343333A (en) * | 1998-06-01 | 1999-12-14 | Nagase Chiba Kk | Epoxy resin composition and its cured product |
| US8168731B2 (en) | 2008-10-22 | 2012-05-01 | Dic Corporation | Curable resin composition, cured product thereof, printed wiring board, epoxy resin, and process for producing the same |
| KR101252063B1 (en) * | 2011-08-25 | 2013-04-12 | 한국생산기술연구원 | Epoxy Compound Having Alkoxysilyl Group, Preparing Method Thereof, Composition Comprising the Same and Cured Product and Use Thereof |
| JP2015502919A (en) * | 2011-11-01 | 2015-01-29 | コリア インスティチュート オブ インダストリアル テクノロジー | Isocyanurate epoxy compound having alkoxysilyl group, process for producing the same, composition containing the same, cured product of the composition, and use of the composition |
| US9902803B2 (en) | 2012-03-14 | 2018-02-27 | Korea Institute Of Industrial Technology | Epoxy compound having alkoxy silyl group, composition comprising same, cured product, use thereof and method for preparing epoxy compound having alkoxy silyl group |
| WO2013151308A1 (en) | 2012-04-02 | 2013-10-10 | 한국생산기술연구원 | Epoxy compound having alkoxysilyl group, composition and hardened material comprising same, use for same, and production method for epoxy compound having alkoxysilyl group |
| KR101863111B1 (en) | 2012-07-06 | 2018-06-01 | 한국생산기술연구원 | Novolac-based epoxy compound, preparing method thereof, composition, cured product thereof, and use thereof |
| JP2014019736A (en) * | 2012-07-13 | 2014-02-03 | Shikoku Chem Corp | Glycidyl isocyanurate compound |
-
2014
- 2014-12-09 KR KR1020140175937A patent/KR101755323B1/en active IP Right Grant
-
2015
- 2015-02-17 JP JP2016553450A patent/JP6423443B2/en active Active
- 2015-02-17 US US15/119,977 patent/US10597412B2/en active Active
- 2015-02-17 CN CN201580020302.8A patent/CN106232608B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336786A (en) * | 1992-12-07 | 1994-08-09 | Shin-Etsu Chemical Company, Limited | Organic silicon compounds |
| JPH06345847A (en) * | 1993-06-07 | 1994-12-20 | Shin Etsu Chem Co Ltd | Epoxy resin composition and semiconductor device |
| KR20130135733A (en) * | 2012-06-01 | 2013-12-11 | 한국생산기술연구원 | Composition and cured product comprising epoxy compound having alkoxysilyl group and inorganic particle, use thereof and preparing method of epoxy compound having alkoxysilyl group |
| WO2014042491A1 (en) * | 2012-09-17 | 2014-03-20 | 한국생산기술연구원 | Epoxy compound having alkoxysilyl group, method for preparing same, composition comprising same, cured product made therefrom, and use thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110121531A (en) * | 2016-12-28 | 2019-08-13 | 三菱瓦斯化学株式会社 | Resin composition for printed circuit board, prepreg, resin sheet, plywood, clad with metal foil plywood, printed circuit board and multilayer board |
| CN110139893A (en) * | 2016-12-28 | 2019-08-16 | 三菱瓦斯化学株式会社 | Prepreg, plywood, clad with metal foil plywood, printed circuit board and multilayer board |
| CN110121531B (en) * | 2016-12-28 | 2021-09-14 | 三菱瓦斯化学株式会社 | Resin composition for printed wiring board, prepreg, resin sheet, laminate, metal foil-clad laminate, and printed wiring board |
| CN110139893B (en) * | 2016-12-28 | 2021-11-19 | 三菱瓦斯化学株式会社 | Prepreg, laminate, metal foil-clad laminate, printed wiring board, and multilayer printed wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106232608B (en) | 2020-03-17 |
| US10597412B2 (en) | 2020-03-24 |
| KR20150098559A (en) | 2015-08-28 |
| JP2017506285A (en) | 2017-03-02 |
| KR101755323B1 (en) | 2017-07-20 |
| JP6423443B2 (en) | 2018-11-14 |
| US20170066789A1 (en) | 2017-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106232608A (en) | Novel epoxide, mixture, compositions and the cured product containing described epoxide, and its preparation method and application | |
| CN104903332B (en) | The application of the preparation method of epoxide, the compound containing alkoxysilyl, the composition comprising the compound, the cured product prepared by said composition and said composition | |
| CN103889977B (en) | There is the epoxide of alkoxysilyl, its preparation method, the compositions including it and curing materials and application thereof | |
| CN105073760B (en) | Epoxide with alkoxysilyl groups, preparation method include its composition and cured product, and application thereof | |
| KR101898526B1 (en) | Epoxy compound having alkoxysilyl group, composition, cured product thereof, use thereof and preparing method of epoxy compound having alkoxysilyl group | |
| CN106103532B (en) | Novolac hardeners and preparation method thereof containing alkoxysilyl, the composition containing curing agent, hardening product and its application | |
| CN104603119B (en) | Epoxides based on novolaks, its preparation method, the compositions comprising this epoxide and cured article and application thereof | |
| JP6461170B2 (en) | Thermosetting resin composition | |
| CN103906753B (en) | Isocyanurate epoxy compound having alkoxysilyl group, method of preparing same, composition including same, cured product of the composition, and use of the composition | |
| CN109053576A (en) | A kind of ionic liquid curing agent and preparation method thereof suitable for epoxy resin | |
| CN108641294A (en) | A kind of fire retarding epoxide resin based on the biradical compound of phospho hetero phenanthrene borate | |
| KR20150105213A (en) | New epoxy compound having alkoxysilyl group, preparing method thereof, composition, cured product thereof, and uses thereof | |
| CN102414242B (en) | Thermosettable resin compositions | |
| JP2007332214A (en) | Thermosetting polymer composition and its cured product | |
| WO2015126143A1 (en) | Novel epoxy compound, mixture, composition, and cured product comprising same, method for preparing same, and use thereof | |
| JP7507259B2 (en) | Phosphorus-containing flame retardant mixture, method for producing said mixture and use of said mixture, and also epoxy resin formulations containing said flame retardant mixture | |
| WO2015105379A1 (en) | Novel novolac hardener having alkoxysilyl group, method for preparing same, composition containing same, hardened product, and use thereof | |
| JP2001114865A (en) | Epoxy resin composition and epoxy resin composition for semiconductor sealing | |
| WO2024135713A1 (en) | Epoxy resin, production method for same, curable resin composition, and cured product | |
| WO2015133840A2 (en) | Epoxy compound having alkoxysilyl group, method for preparing same, composition comprising same, cured product, and use thereof | |
| JPH0269528A (en) | Novel silicone epoxy compound | |
| JPH01275623A (en) | Epoxy resin composition and its cured product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |